KR20170132869A - Photo-alignment composition - Google Patents

Abstract

The invention relates to a composition comprising at least one single photo-alignment polymer, preferably a homopolymer or copolymer, having at least one photoreactive group; And at least one single solvent of formula < RTI ID = 0.0 > I. < / RTI > In addition, the invention relates to the use of the composition in coating or printing, in particular in printing, more particularly ink jet or offset printing processes, most particularly offset printing processes. The present invention also relates to the use of such a photo-alignment composition in the production of an alignment layer for a liquid crystal and in the construction of an unstructured and structured optical element and a multilayer system, particularly a liquid crystal display LCD.
Formula I
(R-CO-O-R ')
In the above formula (I), R and R 'are, independently of each other, straight or branched chain alkyl, provided that at least one alkyl chain is branched.

Description

Photo-alignment composition

The invention relates to a composition comprising at least one single photo-alignment polymer, preferably a homopolymer or copolymer, having at least one photoreactive group; And at least one single solvent of formula < RTI ID = 0.0 > I. < / RTI >

Formula I

(R-CO-O-R ')

In the formula (I)

R and R 'are independently of each other straight or branched chain alkyl, with the proviso that at least one alkyl chain is branched.

In addition, the invention relates to the use of the composition in coating or printing, in particular in printing, more particularly inkjet or offset printing processes, most particularly offset printing processes. The present invention also relates to the use of such photo-alignment compositions in the production of alignment layers for liquid crystals and in the construction of unstructured and structured optical elements and multilayer systems, particularly liquid-crystal display LCDs.

In general, photo-alignment materials are applied with two main techniques, coating and printing.

Coating methods include, for example, spin coating, air doctor coating, blade coating, knife coating, reverse-roll coating, transfer roll coating, gravure roll coating, a kiss roll coating, a cast coating, a spray coating, a slot-orifice coating, a calendar coating, an electrodeposition coating, a dip coating or a die coating.

Printing methods include, for example, lithography such as relief printing such as flexography printing, intaglio printing such as direct gravure printing or offset gravure printing, offset printing, Printing, or stencil printing such as screen printing.

Generally, there are five major printing processes distinguished by the image transfer method and the general type of image carrier used.

Depending on the process, the printed image is transferred directly or indirectly to the substrate. In direct printing, images are transferred directly from the image carrier to the substrate, and examples of direct printing include gravure, flexography, screen printing, and letterpress printing processes. In indirect or offset printing, the image is first transferred from the image carrier to the blanket cylinder and then transferred to the substrate. Lithography, the current dominant printing technology, is an indirect (offset) process.

Image carriers (or plates) can be classified into four types: relief, planographic, intaglio, or screen. In relief printing, the image or printing area rises above the image-free area. Of the five major printing processes, letter press and flexography rely on relief printing. In planar printing, the image area and the area without the image are in the same plane. The image area and the area without the image are defined by different physicochemical properties. Lithography is a flat process. In the intaglio process, the unprinted area is at a common surface level with the substrate while the printing area consisting of the micro etched or engraved wells of different depths and / or sizes is concave. Gravure is an intaglio process. In a screen process (also known as porous printing), the image is transferred to the substrate by pushing the ink through a porous mesh with a picture or character image.

Inkjet printing represents a more robust and robustly growing industrial image deposition process, also called printing, despite considerably different characteristics (e.g., lack of image carriers) compared to the conventional printing processes described above. Ink-jet printers can operate in continuous or drop-on-demand (DOD) mode. In continuous mode, fluid is pumped through the nozzle to form a liquid jet. Periodic perturbations result in uniformly spaced and sized droplets and jet break-up by surface tension. To this end, the fluid must have a certain conductivity. Drop-on-demand is a method of choice in many industries, such as electronics and displays. This is mainly because the droplet size is small, the accuracy is high, and there is no need to use a dopant to make the fluid more conductive. Acoustic pulses inject fluid droplets from the reservoir through the nozzles. The pulses can be generated by heat (bubble-jet) or piezo-electric (piezo-jet). Piezoelectric DOD is generally more suitable for a variety of solvents. The most important part of inkjet printing technology will be the fluid and its properties. Fluid parameters must be optimized on the one hand to reliably obtain droplets during printing to a specific printer (eg, viscosity and surface tension). The fluid must also be optimized to obtain good wetting properties with specific substrates and uniform films.

Flexography technology is used in the LCD industry to successfully apply liquid crystal alignment layers. According to the flexography technique, the liquid crystal alignment layer does not require any etching process and can be directly printed in a predetermined pattern. As generally described, a flexographic process can be a virtually continuous process that uses a series of rollers to transfer a quantity of alignment material onto a desired surface of a substrate (typically glass) in a predetermined pattern. In other words, the flexographic device can be configured to automatically convey a plurality of glass panels sequentially through the process. The apparatus holds a certain amount of the alignment material processing solution using a special resin plate having a series of retention cells arranged in a predetermined pattern. The resin plate is rotated and then directly contacted with the glass panel surface to release the solution, and a predetermined pattern is transferred to form a liquid crystal alignment layer on the surface. The glass panel is then heated to pre-cure the liquid crystal alignment layer.

More specifically, the preparation of a liquid crystal alignment layer by flexographic printing is described next. The alignment material solution is kept on the so-called anilox roll. The anilox roll is preferably plated with chromium, or chromium and nickel (alignment material solution contact surface). A cell having a pyramidal shape is formed at a depth of approximately 20 占 퐉 in the anilox roll so that the alignment material can be retained in the cell.

A doctor roll rotates with the Anilox roll to help uniformly apply the alignment material solution on the surface of the Anilox roll. The resin plate is typically attached to a bottom plate comprising copper. In a preferred embodiment, the resin plate is formed from a polybutadiene resin, such as Asahi Kasei photosensitive resin ("APR"). For convenience of explanation, the resin plate will be hereinafter referred to as an "APR plate ".

The APR plate includes an outer surface of a predetermined pattern. The pattern includes a plurality of cells as an intaglio, such that the alignment material solution can be received within the cell. The depth of the cell is preferably in the range of about 15 to 20 mu m. Therefore, unlike the above general description, a flexographic printer for applying a liquid crystal alignment layer uses an intaglio instead of a relief process.

The alignment material solution is dispensed onto the anilox roll. The Anilox roll and the doctor roll rotate on the outer circumference to make contact. The contact pressure provided by the doctor roll helps the alignment material solution to be evenly distributed in the anilox roll (i. E., Within the cell) and helps bring a certain amount of the solution to fill the cells of the anilox roll. The APR plate is then contacted with the anilox roll to feed or transfer the alignment material solution to the APR plate. Typically, the amount of alignment material solution delivered to the APR plate is determined by the contact force applied by the doctor roll to the anilox roll (or the anilox roll on the doctor roll). The alignment material solution is then retained in the APR plate cell.

An LCD panel or glass is secured to the printing table. At the same time as the copper plate fixing the APR plate rotates, the table advances and the glass moves forward. Thus, the APR plate is in direct contact with the glass substrate, and the alignment material solution is applied to the glass from the cells of the pattern in the APR plate. As a result, an orientation layer is formed on the glass substrate.

There is a tremendous need for photo-alignment compositions because these materials provide access to large-scale fabrication processes that are very efficient and economical. However, their applicability, such as their ability to print, often fails to meet high industry standards. This requires high quality standards such as constant wettability, the desired thickness of the applied layer, and uniformity across the entire surface of the layer.

There is therefore a continuing need for a photo-alignment material that allows for good coating or printing capabilities for the production of thin liquid crystal alignment layers that meet the needs of a uniform surface of zero defect.

In the present invention, the above-mentioned novel photo-alignment compositions which provide access to an improved printing process have been discovered.

Therefore,

a) at least one single photo-alignment polymer, preferably a homopolymer or copolymer, having at least one photoreactive group;

c) further polymers which preferably do not have photoreactive groups, and

b) at least one single solvent of formula < RTI ID = 0.0 >

≪ / RTI >

Formula I

(R-CO-O-R ')

In the formula (I)

R and R 'are independently of each other straight chain alkyl; Preferably straight-chain branched C ₁ -C ₆ alkyl; More preferably a branched C ₁ -C ₆ alkyl, most preferably a branched chain C ₃ -, C ₄ -, C ₅ -, C ₆ alkyl, particularly most preferably a branched C ₄ alkyl; Provided that at least one alkyl chain is branched.

The photo-alignment compositions of the present invention wherein R and R 'are simultaneously branched alkyls are preferred.

The terms provided below in the context of the present invention have the meanings and preferences given below.

"Polymer" means, for example, homopolymers, copolymers, graft polymers, block polymers, highly branched polymers or oligomers; Preferably a polymer or copolymer; Preferred "polymers" of the present invention include, but are not limited to, backbones which are not particularly limited and include, for example, polyamic acids, partially imidized polyamic acids, polyimides, polyamic acid esters, polyesters, polyamides, polysiloxanes, Representative examples include polyacrylates, polyvinyls, cellulose derivatives, polyacetals, polyureas, polyurethanes, polystyrene derivatives, poly (styrene-phenylmaleimide) -derivatives and poly (meth) acrylates, cycloolefin polymers or mixtures thereof do. Most preferred "polymers" are polyamic acid, partially imidized polyamic acid, polyimide, polyamic acid ester, polysiloxane derivatives or mixtures thereof; Polyamic acids, partially imidized polyamic acids, polyimides and mixtures thereof are most preferred and polyamic acids are particularly preferred.

- "Coating" refers to coating techniques, for example coating techniques such as spin-coating, meniscus-coating, wire-coating, slot-coating, Printing, gravure-printing, in particular inkjet or offset printing.

"Photoresistant polymer" means an organic polymer, copolymer or oligomer comprising photoreactive groups capable of withstanding photoresponsivity after irradiation of the alignment light.

"Aligning light" means light of a wavelength capable of initiating light alignment. Preferably, the wavelengths are UV-A, UVB and / or UV / C ranges or visible ranges. This depends on the photo-alignment compound at the appropriate wavelength. Preferably, the photoreactive group is sensitive to visible light and / or UV light. More preferably, the alignment light is at least partially linear, elliptically polarized, e.g., circularly polarized, or non-polarized, most preferably circularly polarized, or obliquely exposed or non- Or at least partially linearly polarized light. In particular, the most preferred alignment light refers to substantially polarized light, especially linearly polarized light; Aligned light refers to non-polarized light applied by oblique illumination.

"Aligning group having the property of controlling alignment of liquid crystal molecules without light irradiation" means an organic group capable of aligning the liquid crystal, preferably capable of aligning the liquid crystal homeotropically or planarly.

Examples of such an alignment group include an unsubstituted or substituted steroidal skeleton, for example, a cholesterol group that is not blocked or blocked by at least one single heteroatom and / or at least one single bridging group, Preferably, the cholesterol group is cholesteryl, cholestanyl, cholestane; Or the alignment group is an unsubstituted or substituted organic chemical structure, which is, for example, 3 to 4 rings selected from any one of 1,4-cyclohexylene and 1,4-phenylene, For example directly coupled or via 1,2-ethylene, the organic chemical structure of which is preferably 3 or 4 pieces of 1,4-cyclohexylene, 3 of 1,4-phenylene Or four pieces or consist of both 1,4-cyclohexylene and 1,4-phenylene, wherein the total number of these pieces is three or four pieces; The substituent is, for example, straight-chain or branched C ₁ -C ₃₀ alkyl.

"Photoreactive group" means an organic group capable of withstanding the reaction after irradiation. For example, photoreactive groups can generate cyclic electron reactions, radical reactions, photoisomerizations, and Norrish reactions, including, for example, dimerizable, resolvable, isomerizable, polymerizable and / A bondable group; More preferably the photoreactive group is selected from the group consisting of cinnamate-, coumarin-, quinoline-, azo-, stilbene-, cyanostilbene-, chalcone-, diphenylacetylene, benzylidene- phthalimidine, benzylideneacetophenone, Phenylene acryloyl, stilbazole and / or an azo group; Most preferably a cinnamate-, coumarin-, quinoline-, cyanostilbene-, and / or chalcone- group; Most preferably a cinnamate- or cyanostilbene group, and even more preferably a cinnamate group.

"Straight-chain alkyl" means, for example, straight chain C ₁ -C ₄₀ alkyl, especially straight chain C ₁ -C ₃₀ alkyl, preferably straight chain C ₁ -C ₂₄ alkyl, more preferably straight C ₁ -C ₁₆ alkyl, Preferably a straight-chain C ₁ -C ₁₀ alkyl, especially most preferably a straight-chain C ₁ -C ₆ alkyl, very particularly preferably most preferably methyl, ethyl, propyl, butyl, pentyl or hexyl; Straight chain C ₁ -C ₁₀ alkyl is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or undecyl; Straight C ₁ -C ₁₆ alkyl is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl.

"Branched alkyl" means, for example, branched chain C ₃ -C ₄₀ alkyl, especially branched C ₃ -C ₃₀ alkyl, preferably branched C ₃ -C ₂₀ alkyl, more preferably branched chain C ₃ - and C ₁₆ alkyl, most preferably branched chain C ₃ -C ₁₀ alkyl, and particularly most preferably a branched chain C ₃ -C ₆ alkyl, which is branched C ₃ -C ₄ -C ₅ -C ₆ alkyl, Very particularly preferably C ₃ -C ₆ alkyl isopropyl, sec-butyl, tert-butyl, isopentyl, dimethylpropyl or 2- methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2 , 2-dimethylbutane.

Branched C ₃ -C ₁₀ alkyl is for example isopropyl, sec-butyl, tert-butyl, isopentyl, dimethylpropyl or 2- methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2 , 2-dimethylbutane isoheptyl, isooctyl, isononyl, isodecyl.

Branched C ₃ -C ₁₆ alkyl is for example isopropyl, sec-butyl, tert-butyl, isopentyl, dimethylpropyl or 2- methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2 Isobutyl, isobutyl, isobutyl, isobutyl, isobutyl, isobutyl, isobutyl, isobutyl, isobutyl, isoheptyl, isoheptyl, isoheptyl, isoheptyl,

Branched C ₃ -C ₂₀ alkyl is for example isopropyl, sec-butyl, tert-butyl, isopentyl, dimethylpropyl or 2- methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2 Isohexadecyl, isoheptadecyl, isooctadecyl, isoheptadecyl, isoheptadecyl, isoheptadecyl, isoheptadecyl, isoheptadecyl, isoheptadecyl, Isonecyl, and isoekosyl.

Branched C ₃ -C ₃₀ alkyl is for example isopropyl, sec-butyl, tert-butyl, isopentyl, dimethylpropyl or 2- methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2 Isohexadecyl, isoheptadecyl, isooctadecyl, isoheptadecyl, isoheptadecyl, isoheptadecyl, isoheptadecyl, isoheptadecyl, isoheptadecyl, Isopentyl, isononyl, isononyl, isononyl, isononyl, isononyl, isononyl, isononyl, isononyl, isononyl, isononyl, isononyl, isononyl, isoquinoxal,

Branched C ₃ -C ₄₀ alkyl is, for example, isopropyl, sec-butyl, tert-butyl, isopentyl, dimethylpropyl, or 2-methylpentane, 3-methylpentane, Isohexadecyl, isoheptadecyl, isooctadecyl, isoheptadecyl, isoheptadecyl, isoheptadecyl, isoheptadecyl, isoheptadecyl, isoheptadecyl, Isopentanoyl, isononyl, isononyl, isononyl, isononyl, isononyl, isononyl, isononyl, isononyl, isononyl, isononyl, isononyl, isoheptanoyl, to be.

(C ₁ -C ₁₂ ) alkylene, preferably C ₁ -C ₆ alkylene, which when used as a single term is branched, straight-chain, substituted, which is unsubstituted, and is unblocked or blocked), and an alicyclic group such as cyclohexylene or C ₁₇ -C ₄₀ aliphatic group, or -Si (R ³⁾ ₂ - or -O-Si (R ³ ) ₂ -, wherein R ³ is C ₁ -C ₂₄ alkylene, preferably at least one C ₁ -C ₆ alkyl, more preferably methyl, ethyl, propyl.

- C ₁ -C ₆ alkylene is, for example, methylene, ethylene, propylene, isopropylene, sec-butylene, tert-butylene, pentylene, isopentylene, hexylene and isohexylene.

C ₁ -C ₃₀ alkyl is preferably C ₁ -C ₃₀ alkyl, more preferably C ₁ -C ₁₆ alkyl, most preferably C ₁ -C ₁₂ alkyl, particularly most preferably C ₁ -C ₆ Alkyl, which is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl. C ₁ -C ₃₀ alkyl has the meaning of straight chain C ₁ -C ₃₀ alkyl and branched C ₃ -C ₃₀ alkyl as described within all the given preferences.

"Alicyclic group" means an unsubstituted or substituted steroidal skeleton, such as a cholesterol group, which is not blocked or is blocked by at least one single heteroatom and / or at least one single bridging group , Preferably the cholesterol group is cholesteryl, cholestanyl, cholestane; Or "alicyclic group" has the meaning of an organic chemical structure, for example, cyclohexylene, especially 1,4-cyclohexylene.

"Bridging group" is -O-, -CH (OH) -, -CO-, -CH 2 (CO) -, -SO-, -CH 2 (SO) -, -S0 2 -, -CH 2 (SO ₂ ) -, -COO-, -OCO-, -COCF ₂ -, -CF ₂ CO, -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -O _{-CO-O, -CH 2 -CH 2} -, -OCH 2 -, -CH 2 O-, -CH = CH-, -C≡C-, -CH = CH-COO-, -OCO-CH = CH -, -CH = N-, -C ( CH 3) = N-, -N = N- or a single bond; Or cyclic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene, wherein one or more C-atoms, -CH- and / or -CH ₂ - groups are, independently of one another, Can be replaced independently by each other.

, -NR¹-, -NR¹-CO-, -CO-NR¹-, -NR¹-CO-O-, -O-CO-NR¹-, -NR¹-CO-NR¹-, -CH=CH-, -C≡C-, -O-CO-O-, 또는 -Si(CH₃)₂-O-Si(CH₃)₂-, 또는 단일 결합의 의미를 갖고, 여기서 R¹은 수소 원자 또는 C₁-C₆알킬을 나타내고, 단, 연결 그룹의 산소 원자는 서로 직접 연결되지 않는다.- "linking group" means -O-, -CO, -CO-O-, -O-CO-,

, -NR ¹ -, -NR ¹ -CO-, -CO-NR ¹ -, -NR ¹ -CO-O-, -O-CO-NR ¹ -, -NR ¹ -CO-NR ¹ - = CH-, -C≡C-, -O-CO -O-, or _{-Si (CH 3) 2 -O-} Si (CH 3) 2 -, or has the meaning of a single bond, wherein R ¹ is hydrogen An atom or a C ₁ -C ₆ alkyl, provided that the oxygen atoms of the connecting group are not directly connected to each other.

Preferably, the invention relates to a photo-alignment composition comprising at least one single photo-alignment polymer, preferably a homopolymer, comprising at least one photo-reactive group.

Also preferably, the present invention relates to a photo-alignment composition comprising at least one single photo-alignment polymer comprising at least two monomers, wherein at least the first monomer comprises a photoreactive group, At least the second monomer comprises a further photoreactive group which is the same as or different from the first monomer, or at least the second monomer does not comprise a photoreactive group and, within the meaning and preference described above, And an alignment group indicating characteristics controlling alignment.

Still further preferably, the present invention relates to a composition comprising at least one monomer having at least one monomer having a photoreactive group and one monomer having an alignment group exhibiting properties controlling the alignment of liquid crystal molecules without light irradiation, Lt; RTI ID = 0.0 > alignment < / RTI > polymers.

Still more preferably, the present invention also relates to a photo-alignment composition comprising at least one single photo-alignment polymer comprising at least two monomers having the same photoreactive groups as the first monomer.

Further, still more preferably, the present invention comprises c) an additional polymer that does not have photoreactive groups, including a backbone that is a polyamic acid, a partially imidized polyamic acid, a polyimide, a polyamic acid ester, or a polysiloxane ≪ RTI ID = 0.0 >

Also within the meaning and preference given above, further preferred are photo-alignment compositions comprising additional polymers without photoreactive groups and preferably having the same backbone as the photo-alignment polymer; Preferably, the main chain is a polyamic acid, a partially imidized polyamic acid, a polyimide, a polyamic acid ester, a polysiloxane, a polysiloxane derivative or a mixture thereof; More preferably, the main chain is a polyamic acid, a partially imidated polyamic acid, a polyimide, and a mixture thereof; Most preferably, the main chain is a polyamic acid; Most particularly preferably, the main chain is more preferably the main chain is a polyamic acid, a polyimide or a mixture thereof.

Preferably, the present invention relates to a photo-alignment composition, wherein the photo-alignment polymer preferably comprises a photoreactive group that is a dimerizable, isomerizable, polymerizable and / or crosslinkable group; More preferably the photoreactive group is selected from the group consisting of cinnamate-, coumarin-, quinoline-, azo-, stilbene-, cyanostilbene-, chalcone-, diphenylacetylene, benzylidenephthalimidine, benzylideneacetophenone, Phenylene acryloyl, stilbazole and / or an azo group; Most preferably a cinnamate-, coumarin-, quinoline-, cyanostilbene-, and / or chalcone- group; Most preferably a cinnamate- or cyano stilbene group, even more preferably a cinnamate group.

More preferably, the present invention relates to

a) at least one single photo-alignment polymer having photoreactive groups,

c) an additional polymer preferably having the same backbone as the photo-alignment polymer,

b) at least one single solvent of formula < RTI ID = 0.0 >

≪ / RTI >

Formula I

(R-CO-O-R ')

In the formula (I)

R and R 'are independently from each other straight chain alkyl; Preferably straight-chain branched C ₁ -C ₆ alkyl; Preferably branched C ₁ -C ₆ alkyl, more preferably branched C ₃ - or C ₄ alkyl, provided that at least one alkyl chain is branched;

Wherein the photo-alignment polymer has photoreactive groups that are cinnamate-, coumarin-, quinoline-, azo-, stilbene-, and / or cyanostilbene- groups; The photo-aligned compounds specifically referred to herein are described in US Re 36625, US 6201087, US 6107427, US 6335409, US 5,965761, US 6277502, US 6649230, US 6833421, US 6831148, US 7514514, US 7750185, US 7994273, US 8436132, US 7687118, US 6340506, US 7959990, US 8173749, US 2011-0065859-A1, US-2010-0048849-A1, US 2010-0266814 A1, US 2012-0316317 A1, US 2013-0035446 A1, US 2014-0162076 A1 , US 2014-0192305 A1, US 2014-0249244 A1, US 2014-0342086 A1, and US 20140162076 Al.

Preferred photopolymerizable polymers cited herein by reference are:

- US Re 36,625, Claim 1-8, more preferably Examples 1-6, Column 7, Line 58- Column 33, Line 8;

- US 6107427, claims, more preferably those listed in Examples 1-9;

- US 5965761, claims 1-7, more preferably those listed in examples 1-6, column 9, line 9 -column 17, line 9;

- US 6277502, Claims 1-4, more preferably Examples 1-5, Column 8, Line 55 - Column 16, Line 37;

- US 6632909, Claims 1-6, more preferably Examples 1-7, Column 9, Line 50-Column 89, Line 24;

- US 6649230, claims, more preferably those listed in Examples 1-4;

- US 6833421, claims, more preferably those listed in Examples 1-9;

- US 7687118, claims, more preferably those listed in Examples 1-18;

Further preferred are photo-alignment polymers of US 817374, US 8329823, and US 8557922, wherein said photo-alignment polymer comprises at least one diamine (I) or at least two diamines, and a tetracarboxylic acid anhydride.

Wherein A is a monocyclic ring of 5 or 6 atoms, two adjacent monocyclic rings of 5 or 6 atoms, a bicyclic ring system of 8, 9 or 10 atoms, or a bicyclic ring system of 13 or 14 atoms An unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from a tricyclic ring system;

Compound residue (Ia), which is the following compound residue of formula (I), represents a straight or branched C ₁ -C ₁₆ fluoroalkyl group,

here,

F is fluorine,

x ₁ is an integer of 1 to 15, preferably an integer of 1 to 10; More preferably 1, 2, 3, 4, 5, 6, 7, 8 or 9, most preferably 3, 4, 5 or 7;

B represents a linear or branched C ₁ -C ₁₆ alkyl group which is unsubstituted or substituted with a substituent selected from the group consisting of di- (C ₁ -C ₁₆ alkyl) amino, C ₁ -C ₆ alkyloxy, nitro, Nitrogen and / or chlorine; Wherein one or more -CH ₂ - groups may each be replaced independently of each other by a linking group;

D represents an unsubstituted or substituted, aliphatic, aromatic and / or alicyclic diamine group having 1 to 40 carbon atoms;

Preferably, D represents an unsubstituted or substituted, aliphatic, aromatic and / or alicyclic diamine group having 1 to 40 carbon atoms, said diamine group having at least one heteroatom and / or bridging group and / or aromatic group and / / RTI > and / or alicyclic groups;

E represents an aromatic group, an oxygen atom, a sulfur atom, -NH-, -N (C ₁ -C ₆ alkyl) -, -CR ² R ³ wherein R ² and R ³ independently of one another are hydrogen or cyclic , Straight-chain or branched, substituted or unsubstituted C ₁ -C ₂₄ alkyl, wherein one or more -CH ₂ - group (s) may be replaced independently of each other by a linking group provided that R ² and R ³ Lt; / RTI > is not hydrogen;

S ¹ and S ² each independently represent a spacer unit;

X and Y are each independently of the other hydrogen, fluorine, chlorine, cyano; C ₁ -C ₁₂ alkyl which is unsubstituted or substituted by fluorine, wherein one or more -CH ₂ - groups may be replaced by a linking group;

n and n1 are each independently 1, 2, 3 or 4, preferably n1 is 1 and n is 1 or 2;

When n is 2, 3 or 4, each of A, B, x ₁ , E, S ¹ , S ² , X and Y is the same or different; when n1 is 2, 3 or 4, each B, x ₁ is the same or different;

Preferably, when n> 1, compound (I) has several side chains, wherein the side chain has the meaning of structure (I) without group D, For example two or three side chains may be connected to one single carbon atom in group D, or they may be connected to group D at different atomic positions within group D, for example at adjacent atomic positions in group D / They can be connected more distantly.

Also,

a) a polymer comprising a diamine (I) and a tetracarboxylic acid dianhydride as a basic building block, more preferably selected from a polyamic acid, a polyamic acid ester, a polyimide or a mixture thereof, At least one < / RTI > single photopolymerizable polymer;

c) It is preferably a polymer comprising diamine (I) tetracarboxylic acid dianhydride as a basic building block, more preferably selected from polyamic acid, polyamic acid ester, polyimide or mixtures thereof, most preferably poly Further polymers which are amic acid; And

b) at least one single solvent of formula < RTI ID = 0.0 >

≪ / RTI > is most preferred.

Formula I

(R-CO-O-R ')

In the formula (I), R and R 'independently of each other are a straight chain alkyl; Preferably straight-chain branched C ₁ -C ₆ alkyl; More preferably a branched C ₁ -C ₆ alkyl, most preferably a branched chain C ₃ -, C ₄ -, C ₅ -, C ₆ alkyl, particularly most preferably a branched C ₄ alkyl; Provided that at least one alkyl chain is branched.

The term "polyimide" in the context of the present invention has the meaning of a polyamic acid or a polyamic acid ester imidized in part or in whole. The term "imidization" has the meaning of partial or total imidization in the context of the present invention.

, -NR¹-, -NR¹-CO-, -CO-NR¹-, -NR¹-CO-O-, -O-CO-NR¹-, -NR¹-CO-NR¹-, -CH=CH-, -C≡C-, -O-CO-O-, 및 -Si(CH₃)₂-O-Si(CH₃)₂-로부터 선택되고, 여기서, R¹은 수소 원자 또는 C₁-C₆알킬을 나타내고; 단, 연결 그룹의 산소 원자는 서로 직접 연결되지 않는다.Further more preferred diamines (I) are those in which the linking group is -O-, -CO, -CO-O-, -O-CO-,

, -NR ¹ -, -NR ¹ -CO-, -CO-NR ¹ -, -NR ¹ -CO-O-, -O-CO-NR ¹ -, -NR ¹ -CO-NR ¹ - = CH-, -C≡C-, -O-CO -O-, and _{-Si (CH 3) 2 -O-} Si (CH 3) 2 - is selected from: wherein, R ¹ is a hydrogen atom or a C ₁ It represents a -C ₆ alkyl; However, the oxygen atoms of the connecting group are not directly connected to each other.

Further more preferred diamines (I) are those wherein the spacer unit is a single bond, cyclic, straight or branched chain, substituted or unsubstituted C ₁ -C ₂₄ alkylene, wherein one or more -CH ₂ - Aromatic, unsubstituted or substituted carbocyclic or heterocyclic groups which may be substituted independently of each other by a linking group and / or connected via a bridging group.

Diamine (I) is added in a more preferred, the bridging group is -CH (OH) -, -CO-, -CH 2 (CO) -, -SO-, -CH 2 (SO) -, -S0 2 -, -CH ₂ (SO ₂ ) -, -COO-, -OCO-, -COCF ₂ -, -CF ₂ CO, -S-CO-, -CO-S-, -SOO-, -OSO-, -O-CO-O, -CH ₂ -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH = CH-, -C≡C-, -CH = CH-COO-, CH = CH-, -CH = N-, -C (CH 3) = N-, -N = N- or selected from or a single bond; Or cyclic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene, wherein one or more -CH ₂ - groups may be replaced independently of one another by a linking group as described above.

An additional, more preferred diamine (I)

D is preferably selected from the formula (III)

^{H (R 5) N- (Sp} 1) k1 - (X 1) t1 - (Z 3 -C 3) a3 - (Z 4 -C 4) a4 - (X 2) t2 - (Sp 2) k2 -N (R < ⁶ >) H (III)

here,

R ⁵ and R ⁶ each independently represent a hydrogen atom or C ₁ -C ₆ alkyl;

Sp ¹ and Sp ² each independently represent unsubstituted or substituted linear or branched C ₁ -C ₂₀ alkylene, wherein one or more -CH ₂ - groups may be replaced independently of one another by a linking group,

k ¹ and k ² are independently an integer having a value of 0 or 1;

X ¹ and X ² each independently represent a linking spacer;

t ¹ and t ² are each independently an integer having a value of 0 or 1;

C ³ and C ⁴ each independently represent a nonaromatic, aromatic, substituted or unsubstituted carbocyclic or heterocyclic group, which may have a side chain T,

Z ³ represents a bridging group;

Z ⁴ represents a substituted or unsubstituted, straight or branched C ₁ -C ₂₀ alkylene group, wherein one or more -CH ₂ - groups are independently of each other a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or hetero By a cyclic group and / or by a heteroatom and / or by a bridging group;

a3 and a4 are independently an integer of 0 to 3, and a3 + a4? 4;

D is linked at least once to at least one group S ¹ of formula (I) through group Sp ¹ and / or group Sp ² ; And / or at least one nonaromatic, aromatic, substituted or unsubstituted carbocyclic or heterocyclic group of group C ³ and / or group C ⁴ ; And / or via at least one side chain T of group C ⁴ and / or group C ³ ; And / or through the group Z ⁴ ; at least one of k ¹ , k ² , a ³ and a ⁴ is not 0; The connecting group and the bridging group are as described above.

Further more preferred diamines (I) are linear or branched C ₁ -C ₂₀ alkylene groups in which the side chain T is substituted or unsubstituted, in which one or more -CH ₂ - group (s) May be replaced by an aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, or by a heteroatom and / or by a bridging group, which may be substituted by at least one group of the formula (I) S ¹ at least once.

Further preferred are the photo-alignment polymers of US 817374, US 8329823, and US 8557922, consisting of at least one diamine compound (I) or at least two different diamines of formula (I)

Here, C ^3, C ⁴ independently is selected from a compound of group G ² with each other, wherein G ² is

및

이고,

And

ego,

"는 전술한 바와 같은 화학식 (III)의 화합물의 인접한 그룹에 대한 C³ 및 C⁴의 연결 결합을 지칭하고;here, "

Quot; refers to a C ³ and C ⁴ linkage to an adjacent group of compounds of formula (III) as described above;

L is _{-CH 3, -COCH 3, -OCH 3} , nitro, cyano, _{halogen, CH 2 = CH-, CH 2} = C (CH 3) -, CH 2 = CH- (CO) O-, CH 2 ^{= CH-O-, -NR 5 R} 6, CH 2 = C (CH 3) - and the _{(CO) O-, CH 2 =} C (CH 3) -O-, where, R ^5, R ⁶ are each to each other Independently represents a hydrogen atom or C ₁ -C ₆ alkyl;

T represents a substituted or unsubstituted, linear or branched C ₁ -C ₂₀ alkylene group, wherein one or more -CH ₂ - groups are independently of each other a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic Can be replaced by a click group or a heteroatom and / or by a bridging group;

m is an integer from 0 to 2;

u1 is an integer from 0 to 4, provided that m + u1 is? 4;

u2 is an integer from 0 to 3, provided that m + u2 is? 3;

and u3 is an integer of 0 to 2, provided that m + u3 is? 2.

An additional, more preferred diamine (I)

D is selected from the group of the following compounds:

및

And

here,

L, L _1, L ₂ and L ₃ are independently from each other _{-CH 3, -COCH 3, -OCH 3} , nitro, cyano, _{halogen, CH 2 = CH-, CH 2} = C (CH 3) -, CH _{2 = CH- (CO) O-,} CH 2 = CH-O-, -NR 5 R 6, CH 2 = C (CH 3) - (CO) O- or _{CH 2 = C (CH 3)} -O- ego,

T, T ₁ , T ₂ and T ₃ independently of one another are a substituted or unsubstituted, linear or branched C ₁ -C ₂₀ alkylene group in which at least one -CH ₂ - group (s) , Aromatic, unsubstituted or substituted carbocyclic or heterocyclic groups and / or by heteroatoms and / or by bridging groups;

"는 단일 결합이고,"

Quot; is a single bond,

q is an integer of 1 or 2;

q1, q2 and q3 are each independently an integer of 0 to 2;

m is an integer of 1 or 2;

m1, m2 and m3 are each independently an integer of 0 to 2;

u3, u3 'and u3' 'are independently of each other an integer from 0 to 2;

R ⁵ and R ⁶ each independently represent a hydrogen atom or C ₁ -C ₆ alkyl;

Z ⁴ represents a substituted or unsubstituted, straight or branched C ₁ -C ₂₀ alkylene group, wherein one or more -CH ₂ - groups are independently of each other a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or hetero By a cyclic group and / or by a heteroatom and / or by a bridging group;

"를 통해, 또는 측쇄 T, T₁, T₂ 또는 T₃을 통해, 또는 그룹 Z⁴를 통해, 화학식 (I)의 적어도 하나의 그룹 S¹에 적어도 1회 연결되며,D is a single bond "

Or at least one group S ¹ of the formula (I) via the side chain T, T ₁ , T ₂ or T ₃ , or via the group Z ⁴ ,

Provided that u3 + q or u3 + m? 4;

u3 + q1 and / or u3 '+ q2 and / or u3 + m1 and / or u3' + m2 or / and u3 '+ q3 or / and u3' + m3?

q1 + q2 and m1 + m2 and q1 + q2 + q3 and m1 + m2 + m3 >

A further more preferred diamine (I) represents a straight or branched C ₁ -C ₁₆ fluoroalkyl group wherein the compound residue of formula (Ia) has -CF ₂ H and -CF ₃ terminal units.

An additional, more preferred diamine (I)

S ¹ and S ² are each independently of the other a single bond or a cyclic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene, wherein one or more -CH ₂ - groups are independently Can be replaced by a group; And / or a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group of formula (IV)

_{^{- (Z 1 -C 1) a1}} - (Z 2 -C 2) a2 - (Z 1a) a3 - (IV)

Wherein C ¹ and C ² each independently represent a nonaromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group,

Z ¹ , Z ² and Z ^1a each independently represent a bridging group,

a1, a2 and a3 each independently represents an integer of 0 to 3, a1 + a2 + a3 ≤ 6, and wherein the bridging groups Z ^1, Z ^1a and Z ² are as defined above.

The photo-alignment polymers of US 817374, US 8329823, and US 8557922, described in Examples 1 to 20, are most preferred;

Tetra carboxylic acid anhydride and at least one diamine compound of the formula (VI), (VII), (VIII), (IX), (X), (XI), (XIa) Most particularly preferred is a photo-alignment polymer comprising at least two diamine compounds of formula (VIII), (IX), (X), (XI), (XIa)

Wherein A, B, x ₁ , n, n ₁ , D, E, S ² , S ¹ , X and Y have the meanings given in claim 1,

R ⁵ , R ⁶ and Z ⁴ have the same meanings as given above;

L is _{-CH 3, -OCH 3, -COCH 3} , nitro, cyano, _{halogen, CH 2 = CH-, CH 2} = C (CH 3) -, CH 2 = CH- (CO) O-, CH 2 and (CO) O-, or _{CH 2 = C (CH 3)} -O-, - = CH-O-, CH 2 = C (CH 3)

u3 is an integer of 0 to 2;

Preferably a diamine of the formula (XII)

Here, x ₁ , B, n, n 1, D, E, S ¹ , X, Y, Z ¹ , L, u ₁ and u ₂ have the same meaning.

More preferably at least one diamine compound selected from the following formulas or at least two diamine compounds:

Where S ¹ has the provided meaning as claimed,

의 화합물 잔기는 직쇄 또는 분지쇄 C₁-C₈플루오르알킬 그룹을 나타내고, 여기서,

Of compound residue refers to a straight chain or branched C ₁ -C ₈ fluoroalkyl group, wherein

F is fluorine,

x ₁ is an integer of 1 to 9,

B represents a linear or branched C ₁ -C ₁₆ alkyl group which is unsubstituted or substituted with a substituent selected from the group consisting of di- (C ₁ -C ₁₆ alkyl) amino, C ₁ -C ₆ alkyloxy, nitro, Nitrogen and / or chlorine; Wherein one or more -CH ₂ - groups are -O-, -CO-, -CO-O-, -O-CO-, -NR 1 -, -NR 1 -CO-, -CO-NR 1 - and -CH = CH-, wherein R ¹ represents a hydrogen atom or a C ₁ -C ₆ alkyl; Provided that the oxygen atoms are not directly connected to each other; The C ₁ -C ₈ fluoroalkyl group has a terminal unit selected from -CF ₂ H, -CF ₃ .

Most particularly preferred photopolymerizable polymers are polymers comprising at least one diamine,

6 - {[((2E) -3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} hexyl 3 , 5-diaminobenzoate

6 - {[((2E) -3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} hexyl 3 , 5-diaminobenzoate

2 - {[((2E) -3- {4- [(4- (trifluoroethoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} ethyl 3,5-diaminobenzo Eight

3 - {[((2E) -3- {4- [(4- (trifluoroethoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} propyl 3,5- diaminobenzo Eight

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} butyl 3,5-diaminobenzoate (prepared by reacting 4 - {[((2E) -3- {4- [4- (trifluoromethoxy) Eight

5 - {[((2E) -3- {4- [4- (trifluoroethoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} pentyl 3,5-diaminobenzo Eight

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} heptyl 3,5-diaminobenzo (2-hydroxyethyl) Eight

8 - {[((2E) -3- {4- [4- (trifluoroethoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} octyl 3,5-diaminobenzo Eight

Benzoyl) oxy} phenyl} prop-2-enoyl) oxy]} undecyl 3,5-diamino-3,3,3,3-tetramethyluronium hexafluorophosphate Benzoate

2 - {[((2E) -3- {4- [(4- (trifluoromethoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} ethyl 3,5-diaminobenzoate

3 - {[((2E) -3- {4- [(4- (trifluoromethoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} propyl 3,5- diaminobenzoate

4 - {[((2E) -3- {4 - [(4- (trifluoromethoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} butyl 3,5-diaminobenzoate

5 - {[((2E) -3- {4- [(4- (trifluoromethoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} pentyl 3,5-diaminobenzoate

6 - {[((2E) -3- {4- [(4- (trifluoromethoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} hexyl 3,5- diaminobenzoate

7 - {[((2E) -3- {4 - [(4- (trifluoromethoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} heptyl 3,5- diaminobenzoate

8 - {[((2E) -3- {4- [(4- (trifluoromethoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} octyl 3,5-diaminobenzoate

2 - {[((2E) -3- {4- [4- (trifluoromethyl) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} ethyl 3,5-diaminobenzoate

3 - {[((2E) -3- {4- [4- (trifluoromethyl) benzoyl) oxy] phenyl} prop-2- enoyl) oxy]} propyl 3,5- diaminobenzoate

4 - {[((2E) -3- {4- [4- (trifluoromethyl) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} butyl 3,5-diaminobenzoate

5 - {[((2E) -3- {4- [(4- (trifluoromethyl) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} pentyl 3,5-diaminobenzoate

6 - {[((2E) -3- {4- [4- (trifluoromethyl) benzoyl) oxy] phenyl} prop-2- enoyl) oxy]} hexyl 3,5- diaminobenzoate

8 - {[((2E) -3- {4- [(4- (trifluoromethyl) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} octyl 3,5-diaminobenzoate

Benzoyl) oxy} phenyl} prop-2-enoyl) oxy]} undecyl 3,5-diaminobenzo (2-hydroxyethyl) Eight

(2E) -3- {4 - [(4- (trifluoroethoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} ethoxy] ethyl 3 , 5-diaminobenzoate

2 {[((2E) -3- {4- [(4- (trifluoroethoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} ethoxy] Ethoxy} ethyl 3,5-diaminobenzoate

(2E) -3- {4- [(4- (trifluoroethoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} propyl 3 , 5-diaminobenzoate

2 - {[((2E) -3- {4 - [(4- (3,3,3-trifluoropropoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} ethyl 3 , 5-diaminobenzoate

Phenyl] prop-2-enoyl) oxy]} propyl 3 (2E) -3- {4- [ , 5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} butyl 3 - {[(2E) -3- {4 - [(4- (3,3,3- trifluoropropoxy) , 5-diaminobenzoate

6 - {[((2E) -3- {4 - [(4- (3,3,3-trifluoropropoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} hexyl 3 , 5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} heptyl 3 (2S) -3 - {[4- (3,3,3-trifluoropropoxy) , 5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} octyl 3 (4-methylphenyl) , 5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} undecyl (3-methylpiperazin-1- 3,5-diaminobenzoate

(2E) -3- {4 - [(4- (3,3,3-trifluoropropoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy] } Ethoxy] ethyl 3,5-diaminobenzoate

2 {2 - {[((2E) -3- {4- [(4- (3,3,3-trifluoropropoxy) benzoyl) oxy] phenyl} prop- Oxy]} ethoxy] ethoxy} ethyl 3,5-diaminobenzoate

2-dimethyl-3 - {[((2E) -3- {4- [4- (3,3,3-trifluoropropoxy) benzoyl) oxy] phenyl} prop- ) Oxy]} propyl 3,5-diaminobenzoate

2 - {[((2E) -3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} ethyl 3 , 5-diaminobenzoate

Phenyl] prop-2-enoyl) oxy]} propyl 3 ((2E) -3- {4- [ , 5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} butyl 3 - {[(2E) -3- {4- [4- (4,4,4- trifluorobutoxy) , 5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} pentyl 3 (2E) -3- {4- [ , 5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} heptyl 3 (2E) -3- {4- [4- (4,4,4- trifluorobutoxy) , 5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} octyl 3 (2E) -3- {4- [ , 5-diaminobenzoate

11 - {[((2E) -3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} undecyl 3,5-diaminobenzoate

(2E) -3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy] } Ethoxy] ethyl 3,5-diaminobenzoate

2 {2 - {[((2E) -3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} prop- Oxy]} ethoxy] ethoxy} ethyl 3,5-diaminobenzoate

2,2-dimethyl-3 - {[((2E) -3- {4- [4- (4,4,4- trifluorobutoxy) benzoyl) oxy] phenyl} prop- ) Oxy]} propyl 3,5-diaminobenzoate

2 - {[((2E) -3- {4- [(4- (5,5,5-trifluorophenoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} ethyl 3 , 5-diaminobenzoate

Phenyl] prop-2-enoyl) oxy]} propyl 3 ((2E) -3- {4- [ , 5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} butyl 3 - {[(2E) -3- {4- [4- (5,5,5- trifluorophenoxy) , 5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} pentyl 3 (2E) -3- {4- [ , 5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} hexyl 3 (4-fluorophenoxy) , 5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} octyl 3 (4-fluorophenoxy) , 5-diaminobenzoate

11 - {[((2E) -3- {4 - [(4- (5,5,5-trifluorophenoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} undecyl 3,5-diaminobenzoate

(2E) -3- {4 - [(4- (5,5,5-trifluorophenoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy] } Ethoxy] ethyl 3,5-diaminobenzoate

2 {[2 - {[(2E) -3- {4- [ Oxy]} ethoxy] ethoxy} ethyl 3,5-diaminobenzoate

Dimethyl-3 - {[((2E) -3- {4- [4- (5,5,5-trifluorophenoxy) benzoyl) oxy] phenyl} prop- ) Oxy]} propyl 3,5-diaminobenzoate

2 - {[((2E) -3- {4 - [(4- (6,6,6- trifluorohexyloxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} ethyl 3,5-diaminobenzoate

3 - {[((2E) -3- {4 - [(4- (6,6,6-trifluorohexyloxy) benzoyl) oxy] phenyl} prop-2-enoyl) 3,5-diaminobenzoate

4 - {[((2E) -3- {4 - [(4- (6,6,6- trifluorohexyloxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} butyl 3,5-diaminobenzoate

5 - {[((2E) -3- {4 - [(4- (6,6,6- trifluorohexyloxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} pentyl 3,5-diaminobenzoate

7 - {[((2E) -3- {4 - [(4- (6,6,6- trifluorohexyloxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} heptyl 3,5-diaminobenzoate

8 - {[((2E) -3- {4 - [(4- (6,6,6- trifluorohexyloxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} octyl 3,5-diaminobenzoate

11 - {[((2E) -3- {4 - [(4- (6,6,6-trifluorohexyloxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} unde 3, 5-diaminobenzoate

2- [2 - {[((2E) -3- {4 - [(4- (6,6,6- trifluorohexyloxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy ]} Ethoxy] ethyl 3,5-diaminobenzoate

2 {2- [2 - {[((2E) -3- {4 - [(4- (6,6,6- trifluorohexyloxy) benzoyl) oxy] phenyl} prop- ) Oxy]} ethoxy] ethoxy} ethyl 3,5-diaminobenzoate

2-dimethyl-3 - {[((2E) -3- {4 - [(4- (6,6,6- trifluorohexyloxy) benzoyl) oxy] phenyl} prop- Yl) oxy]} propyl 3,5-diaminobenzoate

3 - {[((2E) -3- {4- [3-methoxy 4- (3,3,3-trifluoropropoxy) benzoyl) oxy] phenyl} prop- ]} Propyl 3,5-diaminobenzoate

8 - {[((2E) -3- {4- [3-methoxy 4- (3,3,3-trifluoropropoxy) benzoyl) oxy] phenyl} prop- ]} Octyl 3,5-diaminobenzoate

11 - {[((2E) -3- {4- [3-methoxy 4- (3,3,3-trifluoropropoxy) benzoyl) oxy] phenyl} prop- ]} Undecyl 3,5-diaminobenzoate

6 - {[((2E) -3- {4- [3-methoxy 4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} prop- ]} Hexyl 3,5-diaminobenzoate

8 - {[((2E) -3- {4- [3-methoxy 4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} prop- ]} Octyl 3,5-diaminobenzoate

11 - {[((2E) -3- {4- [3-methoxy 4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} prop- ]} Undecyl 3,5-diaminobenzoate

4 - {[((2E) -3- {4- [3-methoxy 4- (5,5,5-trifluorophenoxy) benzoyl) oxy] phenyl} prop- ]} Butyl 3,5-diaminobenzoate

6 - {[((2E) -3- {4- [3-methoxy 4- (5,5,5-trifluorophenoxy) benzoyl) oxy] phenyl} prop- ]} Hexyl 3,5-diaminobenzoate

4 - {[((2E) -3- {4 - [(3-methoxy 4- (6,6,6- trifluorohexyloxy) benzoyl) oxy] phenyl} prop- Oxy]} butyl 3,5-diaminobenzoate

6 - {[((2E) -3- {4 - [(3-methoxy 4- (6,6,6- trifluorohexyloxy) benzoyl) oxy] phenyl} prop- Oxy]} hexyl 3,5-diaminobenzoate

2 - {[((2E) -3- {4 - [(4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy ]} Ethyl 3,5-diaminobenzoate

3 - {[((2E) -3- {4 - [(4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy ]} Propyl 3,5-diaminobenzoate

4 - {[((2E) -3- {4 - [(4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy ]} Butyl 3,5-diaminobenzoate

6 - {[((2E) -3- {4 - [(4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy ]} Hexyl 3,5-diaminobenzoate

7 - {[((2E) -3- {4 - [(4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy ]} Heptyl 3,5-diaminobenzoate

8 - {[((2E) -3- {4 - [(4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy ]} Octyl 3,5-diaminobenzoate

11 - {[((2E) -3- {4 - [(4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy ]} Undecyl 3,5-diaminobenzoate

2- [2 - {[((2E) -3- {4 - [(4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl} prop- Yl) oxy]} ethoxy] ethyl 3,5-diaminobenzoate

2 {2- [2 - {[((2E) -3- {4 - [(4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl} - enyl) oxy]} ethoxy] ethoxy} ethyl 3,5-diaminobenzoate

(2E) -3- {4 - [(4- (4,4,5,5,5-pentafluorophenoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} propyl 3,5-diaminobenzoate

(2E) -3- {4 - [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy] Ethyl 3,5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy] - < / RTI > Propyl 3,5-diaminobenzoate

4 - [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy] Butyl 3,5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy] - < / RTI > Pentyl 3,5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy] - < RTI ID = 0.0 & Hexyl 3,5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy] - < / RTI > Heptyl 3,5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy] - < RTI ID = 0.0 & Octyl 3,5-diaminobenzoate

Benzoyl) oxy] phenyl} prop-2-enoyl) oxy] - < / RTI > Undecyl 3,5-diaminobenzoate

6 - {[((2E) -3- {4- [(4 - {[(4,4,4-trifluorobutoxy) carbonyl] amino} benzoyl) oxy] phenyl} prop- Yl) oxy]} hexyl 3,5-diaminobenzoate

6 - {[((2E) -3- {4 - [(4 - {[(4,4,5,5,5- pentafluorophenoxy) carbonyl] amino} benzoyl) oxy] phenyl} 2-enoyl) oxy]} hexyl 3,5-diaminobenzoate

6 - {[((2E) -3- {4 - [(4 - ({[(4,4,5,5,6,6,6-heptafluorohexyloxy) carbonyl] amino} ) Oxy] phenyl} prop-2-enoyl) oxy]} hexyl 3,5-diaminobenzoate

3,5-diaminobenzyl (2E) 3- {4 - [(4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} acrylate

3,5-diaminobenzyl (2E) 3- {4 - [(4-Trifluoromethoxybenzoyl) oxy] phenyl} acrylate

3,5-diaminobenzyl (2E) 3- {4 - [(4- (2,2,2-trifluoroethoxy) benzoyl) oxy] phenyl} acrylate

3,5-diaminobenzyl (2E) 3- {4 - [(4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] phenyl} acrylate

3,5-diaminobenzyl (2E) 3- {4 - [(4- (4,4,5,5,5-pentafluoropentyloxy) benzoyl) oxy] phenyl} acrylate

3,5-diaminobenzyl (2E) 3- {4 - [(4- (3,3,4,4,5,5,6,6,6-nonafluorohexyloxy) benzoyl) oxy] phenyl } Acrylate

3,5-diaminobenzyl (2E) 3- {4- [(4- (2,2,3,3,3-pentafluoropropyloxy) benzoyl) oxy] phenyl} acrylate

3,5-diaminobenzyl (2E) 3- {4 - [(4- (2,2,3,4,4,4-hexafluorobutoxy) benzoyl) oxy] phenyl} acrylate

3,5-diaminobenzyl (2E) 3- {4 - [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} acrylate

3,5-diaminobenzyl (2E) 3- {4- [(4- (1,1,2,2-tetrafluoropropoxy) benzoyl) oxy] phenyl} acrylate

3,5-diaminobenzyl (2E) 3- {4 - [(4- (4,4,5,5,6,6,6-heptafluorohexyloxy) benzoyl) oxy] phenyl} acrylate

3,5-diaminobenzyl (2E) 3- {4- [4- (4,5,5,5-tetrafluoro-4- (trifluoromethyl) pentyloxy) benzoyl) oxy] phenyl} Rate

3,5-diaminobenzyl (2E) 3- {4 - {[(4- (4,4,5,5,6,6,6-heptafluorohexyloyl) oxy) benzoyloxy] phenyl} Rate

3,5-diaminobenzyl (2E) 3- {4 - [(4 - [(4,4,4-trifluorobutoxy) carbonyl] amino) benzoyl) oxy] phenyl} acrylate

3,5-diaminobenzyl (2E) 3- {4 - [(4 - [(4,4,4-trifluoropentyloxy) carbonyl] amino) benzoyl] oxy} phenyl} acrylate

3,5-diaminobenzyl (2E) 3- {4- [4- (4,4,5,5,5-pentafluoropentyloyloxy) benzoyloxy] phenyl} acrylate

3,5-diaminobenzyl (2E) 3- {4- [4- (4,4,5,5,6,6,6-heptafluorohexyloyloxy) benzoyloxy] phenyl} acrylate

3,5-diaminobenzyl (2E) 3- {4 - [(3-fluoro-4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} acrylate

2,5-diaminobenzyl (2E) 3- {4 - [(4-Trifluoromethoxybenzoyl) oxy] phenyl} acrylate

2,5-diaminobenzyl (2E) 3- {4- [(4- (2,2,2-trifluoroethoxy) benzoyl) oxy] phenyl} acrylate

2,5-diaminobenzyl (2E) 3- {4 - [(4- (5,5,5-trifluorobutoxy) benzoyl) oxy] phenyl} acrylate

2,5-diaminobenzyl (2E) 3- {4 - [(4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] phenyl} acrylate

2,5-diaminobenzyl (2E) 3- {4 - [(4- (4,4,5,5,5-pentafluoropentyloxy) benzoyl) oxy] phenyl} acrylate

2,5-diaminobenzyl (2E) 3- {4- [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} acrylate

2,5-diaminobenzyl (2E) 3- {4 - [(4- (1,1,2,2-tetrafluoropropoxy) benzoyl) oxy] phenyl} acrylate

2,5-diaminobenzyl (2E) 3- {4 - [(4- (4,4,5,5,6,6,6-heptafluorohexyloxy) benzoyl) oxy] phenyl} acrylate

2,5-diaminobenzyl (2E) 3- {4 - {[(4- (4,4,5,5,6,6,6-heptafluorohexyloyl) oxy) benzoyloxy] phenyl} Rate

2,5-diaminobenzyl (2E) 3- {4- [(4 - [(4,4,4-trifluorobutoxy) carbonyl] amino) benzoyl) oxy] phenyl} acrylate

2,5-diaminobenzyl (2E) 3- {4 - [(4 - [(4,4,4-trifluoropentyloxy) carbonyl] amino) benzoyl) oxy] phenyl} acrylate

2,5-diaminobenzyl (2E) 3- {4- [4- (4,4,5,5,5-pentafluoropentyloyloxy) benzoyloxy] phenyl} acrylate

2,5-diaminobenzyl (2E) 3- {4- [4- (4,4,5,5,6,6,6-heptafluorohexyloyloxy) benzoyloxy] phenyl} acrylate

2,5-diaminobenzyl (2E) 3- {4 - [(2-fluoro-4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} acrylate

2,4-diaminobenzyl (2E) 3- {4 - [(4-Trifluoromethoxybenzoyl) oxy] phenyl} acrylate

2,4-diaminobenzyl (2E) 3- {4 - [(4- (2,2,2-Trifluoroethoxy) benzoyl) oxy] phenyl} acrylate

2,4-diaminobenzyl (2E) 3- {4 - [(4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] phenyl} acrylate

2,4-diaminobenzyl (2E) 3- {4 - [(4- (4,4,4-Trifluorobutoxy) benzoyl) oxy] phenyl} acrylate

2,4-diaminobenzyl (2E) 3- {4 - [(4- (4,4,5,5,5-pentafluoropentyloxy) benzoyl) oxy] phenyl} acrylate

2,4-diaminobenzyl (2E) 3- {4 - [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} acrylate

2,4-diaminobenzyl (2E) 3- {4 - [(4- (1,1,2,2-tetrafluoropropoxy) benzoyl) oxy] phenyl} acrylate

2,4-diaminobenzyl (2E) 3- {4 - [(4- (4,4,5,5,6,6,6-heptafluorohexyloxy) benzoyl) oxy] phenyl} acrylate

2,4-diaminobenzyl (2E) 3- {4 - {[(4- (4,4,5,5,6,6,6-heptafluorohexyloyl) oxy) benzoyloxy] phenyl} Rate

2,4-diaminobenzyl (2E) 3- {4- [(4 - [(4,4,4-trifluorobutoxy) carbonyl] amino) benzoyl) oxy] phenyl} acrylate

2,4-diaminobenzyl (2E) 3- {4 - [(4 - [(4,4,4-Trifluoropentyloxy) carbonyl] amino) benzoyl) oxy] phenyl} acrylate

2,4-diaminobenzyl (2E) 3- {4- [4- (4,4,5,5,5-pentafluoropentyloyloxy) benzoyloxy] phenyl} acrylate

2,4-diaminobenzyl (2E) 3- {4- [4- (4,4,5,5,6,6,6-heptafluorohexyloyloxy) benzoyloxy] phenyl} acrylate

2,4-diaminobenzyl (2E) 3- {4 - [(3-fluoro-4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [(4-trifluoromethoxybenzoyl) oxy] phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [(4- (2,2,2-trifluoroethoxy) benzoyl) oxy] phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,4-trifluorobutanoyl) oxy) benzoyl] oxy} phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [(3-methoxy-4- trifluoromethoxybenzoyl) oxy] phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [3-methoxy 4- (2,2,2-trifluoroethoxy) benzoyl) oxy] phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [3-methoxy 4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [3-methoxy 4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [3-methoxy 4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl } Acrylate

2- (3-methoxy-4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} acrylate Rate

(2E) 3- {4 - [(3-methoxy 4- (4,4,4-trifluorobutenoyl) oxy) benzoyl] oxy} phenyl} acrylate Rate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [(4-trifluoromethoxybenzoyl) oxy] -3-methoxyphenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4 - [(4- (2,2,2- trifluoroethoxy) benzoyl) oxy] -3-methoxyphenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] -3- methoxyphenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4 - [(4- (5,5,5- trifluoropentyloxy) benzoyl) oxy] -3-methoxyphenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] -3- Phenyl} acrylate

(2E) 3- {4 - [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] -3-methoxyphenyl} Acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,4-trifluorobutanoyl) oxy] benzoyl] oxy} -3-methoxyphenyl} Acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [(4-trifluoromethoxyphenoxy) carbonyl] phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [4- (2,2,2-trifluoroethoxy) phenoxy) carbonyl] phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,4-trifluorobutoxy) phenoxy) carbonyl] phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [4- (5,5,5-trifluoropentyloxy) phenoxy) carbonyl] phenyl} acrylate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,5,5,5-pentafluorophenoxy) phenoxy) carbonyl] phenyl} Rate

2- (3,5-diaminophenyl) ethyl (2E) 3- {4- [4- (1,1,2,2-tetrafluoroethoxy) phenoxy) carbonyl] phenyl} acrylate

2- (2,5-diaminophenyl) ethyl (2E) 3- {4- [(4-trifluoromethoxybenzoyl) oxy] phenyl} acrylate

2- (2,5-diaminophenyl) ethyl (2E) 3- {4- [(4- (2,2,2-trifluoroethoxy) benzoyl) oxy] phenyl} acrylate

2- (2,5-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} acrylate

2- (2,5-diaminophenyl) ethyl (2E) 3- {4- [4- (5,5,5- trifluoropentyloxy) benzoyl) oxy] phenyl} acrylate

2- (2,5-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl} acrylate

2- (2,5-diaminophenyl) ethyl (2E) 3- {4- [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} acrylate

2- (2,5-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,4-trifluorobutanoyl) oxy] benzoyl] oxy] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [(4-trifluoromethoxybenzoyl) oxy] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [(4- (2,2,2-trifluoroethoxy) benzoyl) oxy] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [(4- (2,2,3,3,3-pentafluoropropyloxy) benzoyl) oxy] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4 - [(4- (2,2,3,4,4,4- hexafluorobutoxy) benzoyl) oxy] phenyl} Rate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4 - [(4- (3,3,4,4,5,5,6,6,6-nonafluorohexyloxy) Benzoyl) oxy] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [(4- (1,1,2,2-tetrafluoropropoxy) benzoyl) oxy] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4 - [(4- (4,4,5,5,6,6,6-heptafluorohexyloxy) benzoyl) oxy] Phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [4- (5,5,6,6-pentafluorohexyl) benzoyl) oxy] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,4-trifluorobutanoyl) oxy] benzoyl] oxy} phenyl} acrylate

Phenyl] 4- (4, 4, 4-trifluoro-2-oxo-propyl) Lt; / RTI > benzoate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [3-fluoro-4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl}

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [4- (5,5,5-trifluorophenoxy) benzoyl) oxy] phenyl} acrylate

(2E) 3- {4 - [(3,4-di (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,5,5,5-pentafluorophenoxycarbonyl) phenoxy) carbonyl] phenyl } Acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [(4 - [(4,4,4-trifluorobutoxy) carbonyl] amino) benzoyl) oxy] phenyl} Rate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4 - [(4 - [(4,4,5,5,5- pentafluorophenoxy) carbonyl] amino) benzoyl) oxy ] Phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [(3-methoxy-4-trifluoromethoxybenzoyl) oxy] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [3-methoxy 4- (2,2,2-trifluoroethoxy) benzoyl) oxy] phenyl}

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [3-methoxy 4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4 - [(3-methoxy 4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4 - [(3-methoxy 4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl } Acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [3-methoxy 4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] Rate

(2E) 3- {4 - [(3-methoxy 4- (4,4,4-trifluorobutenoyl) oxy) benzoyl] oxy} phenyl} acrylate Rate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] -3- methoxyphenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] -3- methoxyphenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] -3- Phenyl} acrylate

(2E) 3- {4 - [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] -3-methoxyphenyl} Acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,4-trifluorobuteno) oxy) benzoyl] oxy} -3-methoxyphenyl} Acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,4-trifluorobutoxy) phenoxy) carbonyl] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [4- (5,5,5-trifluoropentyloxy) phenoxy) carbonyl] phenyl} acrylate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [4- (4,4,5,5,5- pentafluorophenoxy) phenoxy) carbonyl] phenyl} Rate

2- (2,4-diaminophenyl) ethyl (2E) 3- {4- [(4- (1,1,2,2-tetrafluoroethoxy) phenoxy) carbonyl] phenyl} acrylate

3- (3,5-diaminophenyl) propyl (2E) 3- {4- [(4-trifluoromethoxybenzoyl) oxy] phenyl} acrylate

3- (3,5-diaminophenyl) propyl (2E) 3- {4- [(4- (2,2,2-trifluoroethoxy) benzoyl) oxy] phenyl} acrylate

3- (3,5-diaminophenyl) propyl (2E) 3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} acrylate

3- (3,5-diaminophenyl) propyl (2E) 3- {4- [(4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] phenyl} acrylate

3- (3,5-diaminophenyl) propyl (2E) 3- {4- [4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl} acrylate

3- (3,5-diaminophenyl) propyl (2E) 3- {4- [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} acrylate

3- (3,5-diaminophenyl) propyl (2E) 3- {4- [4- (4,4,4-trifluorobutanoyl) oxy) benzoyl] oxy} phenyl} acrylate

3- (2,4-diaminophenyl) propyl (2E) 3- {4- [(4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} acrylate

3- (2,4-diaminophenyl) propyl (2E) 3- {4- [4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] phenyl} acrylate

3- (2,4-diaminophenyl) propyl (2E) 3- {4- [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} acrylate

3- (2,4-diaminophenyl) propyl (2E) 3- {4- [4- (4,4,4-trifluorobuteno) oxy) benzoyl] oxy} phenyl} acrylate

(2E) 3- {4 - [(4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} acrylate

(2E) 3- {4 - [(4- (4,4,5,5,5-pentafluorophenoxy) benzoyl) oxy] phenyl} acrylate

(2E) 3- {4 - [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} acrylate

(4E, 4-trifluorobutoxy) benzoyl) oxy] phenyl} propan-2-ol -2-ethoxy] propane diol

(2E) 3- {4- [(4-trifluoromethoxybenzoyl) oxy] phenyl} prop-2-enoyl] propanediol

(2E) 3- {4 - [(4- (2,2,2-trifluoroethoxy) benzoyl) oxy] phenyl} propane -2-ethanoyl] propanediol

(2E) 3- {4 - [(4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} propane -2-ethanoyl] propanediol

(2E) 3- {4 - [(4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] phenyl} propane -2-ethanoyl] propanediol

(2E) 3- {4 - [(4- (4,4,5,5,5-pentafluorophenoxy) benzoyl) oxy] Phenyl} prop-2-enoyl] propanediol

(2E) 3- {4 - [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} Prop-2-enoyl] propanediol

Benzoyl] oxy} phenyl} -1,3-di [(2E) -3- {4 - [(4- (4,4,4- trifluorobutenoyl) oxy) Prop-2-enoyl] propanediol

(2E) 3- {4 - [(3-methoxy-4-trifluoromethoxybenzoyl) oxy] phenyl} prop-2-eno Typical propanediol

(2E) 3- {4 - [(3-methoxy 4- (2,2,2-trifluoroethoxy) benzoyl) oxy] Phenyl} prop-2-enoyl] propanediol

(2E) 3- {4 - [(3-methoxy 4- (4,4,4-trifluorobutoxy) benzoyl) oxy] Phenyl} prop-2-enoyl] propanediol

(2E) 3- {4 - [(3-methoxy 4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] Phenyl} prop-2-enoyl] propanediol

(2E) 3- {4 - [(3-methoxy 4- (4,4,5,5,5-pentafluorophenoxy) Benzoyl) oxy] phenyl} prop-2-enoyl] propanediol

(2E) 3- {4 - [(3-methoxy 4- (1,1,2,2-tetrafluoroethoxy) benzoyl) Oxy] phenyl} prop-2-enoyl] propanediol

(2E) 3- {4 - [(3-methoxy 4- (4,4,4-trifluorobutanoyl) oxy) benzoyl] Oxy} phenyl} prop-2-enoyl] propanediol

3-methoxyphenyl) prop-2-ene (prepared by reacting 2,2-bis (4-aminobenzyl) Typical propanediol

(2E) 3- {4 - [(4- (2,2,2-trifluoroethoxy) benzoyl) oxy] -3- Propoxyphenyl} prop-2-enoyl] propanediol

(2E) 3- {4 - [(4- (4,4,4-trifluorobutoxy) benzoyl) oxy] -3- Propoxyphenyl} prop-2-enoyl] propanediol

(2E) 3- {4 - [(4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] -3- Propoxyphenyl} prop-2-enoyl] propanediol

(2E) 3- {4 - [(4- (4,4,5,5,5-pentafluorophenoxy) benzoyl) oxy] -3-methoxyphenyl} prop-2-enoyl] propanediol

(2E) 3- {4 - [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] -3 -Methoxyphenyl} prop-2-enoyl] propanediol

Benzoyl] oxy} -3 (4-trifluoromethylbenzoyl) -1,3-di [(2E) -Methoxyphenyl} prop-2-enoyl] propanediol

Propyl-2-enoyl] propane-2-carbonyl] propane-2- Dior

(2E) 3- {4 - [(4- (2,2,2-trifluoroethoxy) phenoxy) carbonyl] phenyl} Prop-2-enoyl] propanediol

(4E, 4-trifluorobutoxy) phenoxy) carbonyl] phenyl} -1,3-di [ Prop-2-enoyl] propanediol

(4-aminobenzyl) -1,3-di [(2E) -3- {4- [4- (5,5,5-trifluoropentyloxy) phenoxy) carbonyl] phenyl} Prop-2-enoyl] propanediol

(2E) 3- {4 - [(4- (4,4,5,5,5-pentafluorophenoxy) phenoxy) carbo Yl] phenyl} prop-2-enoyl] propanediol

(2E) 3- {4 - [(4- (1,1,2,2-tetrafluoroethoxy) phenoxy) carbonyl] Phenyl} prop-2-enoyl] propanediol

6 - {[((2E) -3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} prop-2-enoyl) oxy]} hexyl

4- [6 - {[((2E) -3- {4- [4- (4,4,4- trifluorobutoxy) benzoyl) oxy] phenyl} prop- 2-enoyl) oxy]} hexyloxy] benzoate

Benzoyl) oxy] phenyl} prop-2-enoyl] methyl 4, 4-dihydro- 4'-diamino 1,1'-biphenyl

(2E) 3- {4 - [(4-trifluoromethoxybenzoyl) oxy] phenyl} prop-2-enoyl] methyl 4,4'- diamino 1,1'- Biphenyl

(2E) 3- {4- [(4- (2,2,2-trifluoroethoxy) benzoyl) oxy] phenyl} prop- 2-enoyl] methyl 4,4 '-Diamino 1,1'-biphenyl

(2E) 3- {4 - [(4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} prop- 2-enoyl] methyl 4,4 '-Diamino 1,1'-biphenyl

Benzoyl) oxy] phenyl} prop-2-enoyl] methyl 4, 4-dihydroxypropyl) '-Diamino 1,1'-biphenyl

(2E) 3- {4 - [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} prop-2-enoyl] methyl 4 , 4'-diamino 1,1'-biphenyl

Benzoyl] oxy} phenyl] prop-2-enoyl] methyl 4 (trifluoromethyl) , 4'-diamino 1,1'-biphenyl

(2E) 3- {4 - [(3-methoxy-4-trifluoromethoxybenzoyl) oxy] phenyl} prop-2-enoyl] methyl 4,4'-diamino 1,1'-biphenyl

(2E) 3- {4 - [(3-methoxy 4- (2,2,2-trifluoroethoxy) benzoyl) oxy] phenyl} prop- Methyl 4,4'-diamino 1,1'-biphenyl

(2E) 3- {4 - [(3-methoxy 4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} prop- Methyl 4,4'-diamino 1,1'-biphenyl

(2E) 3- {4- [(3-methoxy 4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] phenyl} prop- Methyl 4,4'-diamino 1,1'-biphenyl

(2E) 3- {4 - [(3-methoxy 4- (4,4,5,5,5-pentafluorophenoxy) benzoyl) oxy] phenyl} -Enoyl] methyl 4,4'-diamino 1,1'-biphenyl

(2E) 3- {4 - [(3-methoxy 4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} prop- Yl] methyl 4,4'-diamino 1,1'-biphenyl

(2E) 3- {4 - [(3-methoxy 4- (4,4,4-trifluorobutanoyl) oxy) benzoyl] oxy} phenyl] prop- Yl] methyl 4,4'-diamino 1,1'-biphenyl

3-methoxyphenyl} prop-2-enoyl] methyl 4,4'-diamino (3-methoxybenzoyl) 1,1'-biphenyl

(2E) 3- {4- [(4- (2,2,2-trifluoroethoxy) benzoyl) oxy] -3-methoxyphenyl} prop- ] Methyl 4,4'-diamino 1,1'-biphenyl

(2E) 3- {4 - [(4- (4,4,4-trifluorobutoxy) benzoyl) oxy] -3-methoxyphenyl} prop- ] Methyl 4,4'-diamino 1,1'-biphenyl

(2E) 3- {4 - [(4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] -3-methoxyphenyl} prop- ] Methyl 4,4'-diamino 1,1'-biphenyl

(2E) 3- {4 - [(4- (4,4,5,5,5-pentafluorophenoxy) benzoyl) oxy] -3-methoxyphenyl} prop- 2-enoyl] methyl 4,4'-diamino 1,1'-biphenyl

Bis [(2E) 3- {4 - [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] -3- methoxyphenyl} Enoyl] methyl 4,4'-diamino 1,1'-biphenyl

Oxy] benzoyl] oxy} -3-methoxyphenyl] prop-2-ene [ Enoyl] methyl 4,4'-diamino 1,1'-biphenyl

(2E) 3- {4 - [(4-trifluoromethoxyphenoxy) carbonyl] phenyl} prop-2-enoyl] methyl 4,4'-diamino 1,1'- '-Biphenyl

(2E) 3- {4- [(4- (2,2,2-trifluoroethoxy) phenoxy) carbonyl] phenyl} prop-2-enoyl] methyl 4 , 4'-diamino 1,1'-biphenyl

Carbonyl] phenyl} prop-2-enoyl] methyl 4 (trifluoromethyl) , 4'-diamino 1,1'-biphenyl

[4 - [(E) -3- [4- [4- (4,4,4-Trifluorobutoxy) Phenyl] methoxy] -3-oxo-prop-1-enyl] phenyl] -4- (4,4,4-trifluoro Lt; / RTI > benzoate

(2E) 3- {4- [(4- (5,5,5-trifluoropentyloxy) phenoxy) carbonyl] phenyl} prop-2-enoylmethyl 4, 4'-diamino 1,1'-biphenyl

(2E) 3- {4 - [(4- (4,4,5,5,5-pentafluorophenoxy) phenoxy) carbonyl] phenyl} prop-2-eno Yl] methyl 4,4'-diamino 1,1'-biphenyl

(2E) 3- {4- [(4- (1,1,2,2-tetrafluoroethoxy) phenoxy) carbonyl] phenyl} prop-2-enoyl] Methyl 4,4'-diamino 1,1'-biphenyl

2- (2,4-diaminophenyl) -1,3 di [(2E) -3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} -2-ethoxy] propane diol

2- (2,4-diaminophenyl) -1,3 di [(2E) -3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} -2-ethoxy] propane diol

2- (2,4-diaminophenyl) -1,3 di [(2E) 3- {4 - [(4-trifluoromethoxybenzoyl) oxy] phenyl} prop-

2- (2,4-diaminophenyl) -1,3 di [(2E) -3- {4 - [(4- (2,2,2- trifluoroethoxy) benzoyl) oxy] phenyl} -2-ethanoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) -3- {4- [4- (4,4,4- trifluorobutoxy) benzoyl) oxy] phenyl} propyl -2-ethanoyl] propanediol

(2,4-diaminophenyl) -1,3 di [(2E) 3- {4- [4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] phenyl} propyl -2-ethanoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) 3- {4 - [(4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] Phenyl} prop-2-enoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) -3- {4 - [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) Prop-2-enoyl] propanediol

(2,4-diaminophenyl) -1,3 di [(2E) -3- {4- [4- (4,4,4-trifluorobutanoyl) oxy) benzoyl] oxy} phenyl} Prop-2-enoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) 3- {4 - [(3-methoxy-4- trifluoromethoxybenzoyl) oxy] phenyl} prop- Typical propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) -3- {4 - [(3-methoxy 4- (2,2,2- trifluoroethoxy) benzoyl) oxy] Phenyl} prop-2-enoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) -3- {4 - [(3-methoxy 4- (4,4,4- trifluorobutoxy) benzoyl) oxy] Phenyl} prop-2-enoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) -3- {4 - [(3-methoxy 4- (5,5,5- trifluoropentyloxy) benzoyl) oxy] Phenyl} prop-2-enoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) 3- {4 - [(3-methoxy 4- (4,4,5,5,5- pentafluorophenoxy) Benzoyl) oxy] phenyl} prop-2-enoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) -3- {4 - [(3-methoxy 4- (1,1,2,2-tetrafluoroethoxy) benzoyl) Oxy] phenyl} prop-2-enoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) -3- {4 - [(3-methoxy 4- (4,4,4- trifluorobuteno) oxy) benzoyl] Oxy} phenyl} prop-2-enoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) 3- {4 - [(4-trifluoromethoxybenzoyl) oxy] -3-methoxyphenyl} prop- Typical propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) 3- {4- [(4- (2,2,2- trifluoroethoxy) benzoyl) oxy] -3- Propoxyphenyl} prop-2-enoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) -3- {4- [4- (4,4,4- trifluorobutoxy) benzoyl) oxy] -3- Propoxyphenyl} prop-2-enoyl] propanediol

(2E) 3- {4 - [(4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] -3- Propoxyphenyl} prop-2-enoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) 3- {4 - [(4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] -3-methoxyphenyl} prop-2-enoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) 3- {4 - [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] -3 -Methoxyphenyl} prop-2-enoyl] propanediol

(2,4-diaminophenyl) -1,3 di [(2E) -3- {4 - [(4- (4,4,4- trifluorobutenoyl) oxy) benzoyl] oxy} -Methoxyphenyl} prop-2-enoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) 3- {4 - [(4-trifluoromethoxyphenoxy) carbonyl] phenyl} prop- Dior

2- (2,4-diaminophenyl) -1,3 di [(2E) 3- {4- [(4- (2,2,2- trifluoroethoxy) phenoxy) carbonyl] phenyl} Prop-2-enoyl] propanediol

Phenyl] -1,3 di [(2E) -3- {4 - [(4- (4,4,4-trifluorobutoxy) phenoxy) carbonyl] phenyl} Prop-2-enoyl] propanediol

Phenyl] -1,3 di [(2E) -3- {4- [(4- (5,5,5-trifluoropentyloxy) phenoxy) carbonyl] phenyl} Prop-2-enoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) 3- {4- [4- (4,4,5,5,5- pentafluorophenoxy) phenoxy) Yl] phenyl} prop-2-enoyl] propanediol

2- (2,4-diaminophenyl) -1,3 di [(2E) -3- {4 - [(4- (1,1,2,2-tetrafluoroethoxy) phenoxy) carbonyl] Phenyl} prop-2-enoyl] propanediol

2- (3,5-diaminophenyl) -1,3 di [(2E) 3- {4 - [(4-trifluoromethoxybenzoyl) oxy] phenyl} prop-

(2E) 3- {4 - [(4- (2,2,2-trifluoroethoxy) benzoyl) oxy] phenyl} propane -2-ethanoyl] propanediol

2- (3,5-diaminophenyl) -1,3 di [(2E) -3- {4- [4- (4,4,4-trifluorobutoxy) benzoyl) oxy] phenyl} -2-ethanoyl] propanediol

Phenyl] propyl) -1,3-di [(2E) -3- {4- [4- (5,5,5-trifluoropentyloxy) benzoyl) -2-ethanoyl] propanediol

2- (3,5-diaminophenyl) -1,3 di [(2E) -3- {4 - [(4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] Phenyl} prop-2-enoyl] propanediol

Phenyl] -1,3 di [(2E) -3- {4- [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] phenyl} Prop-2-enoyl] propanediol

Benzoyl] oxy} phenyl} -1,3-di [(2E) -3- {4 - [(4- (4,4,4- trifluorobutenoyl) oxy) Prop-2-enoyl] propanediol

2- (3,5-diaminophenyl) -1,3 di [(2E) 3- {4 - [(3-methoxy-4- trifluoromethoxybenzoyl) oxy] phenyl} prop- Typical propanediol

2- (3,5-diaminophenyl) -1,3 di [(2E) -3- {4 - [(3-methoxy 4- (2,2,2- trifluoroethoxy) benzoyl) oxy] Phenyl} prop-2-enoyl] propanediol

3- (4-methoxy-4- (4,4,4-trifluorobutoxy) benzoyl) oxy] -1,3-di [ Phenyl} prop-2-enoyl] propanediol

2- (3,5-diaminophenyl) -1,3 di [(2E) -3- {4 - [(3-methoxy 4- (5,5,5- trifluoropentyloxy) benzoyl) oxy] Phenyl} prop-2-enoyl] propanediol

2- (3,5-diaminophenyl) -1,3 di [(2E) 3- {4 - [(3-methoxy 4- (4,4,5,5,5- pentafluorophenoxy) Benzoyl) oxy] phenyl} prop-2-enoyl] propanediol

2- (3,5-diaminophenyl) -1,3 di [(2E) -3- {4 - [(3-methoxy 4- (1,1,2,2-tetrafluoroethoxy) benzoyl) Oxy] phenyl} prop-2-enoyl] propanediol

2- (3,5-diaminophenyl) -1,3 di [(2E) 3- {4 - [(3-methoxy 4- (4,4,4- trifluorobutanoyl) oxy) benzoyl] Oxy} phenyl} prop-2-enoyl] propanediol

3- (4-trifluoromethoxybenzoyl) oxy] -3-methoxyphenyl} prop-2-ene Typical propanediol

2- (3,5-diaminophenyl) -1,3 di [(2E) 3- {4 - [(4- (2,2,2- trifluoroethoxy) benzoyl) oxy] -3- Propoxyphenyl} prop-2-enoyl] propanediol

2- (3,5-diaminophenyl) -1,3 di [(2E) -3- {4- [4- (4,4,4- trifluorobutoxy) benzoyl) oxy] -3- Propoxyphenyl} prop-2-enoyl] propanediol

3- (4 - [(4- (5,5,5-trifluoropentyloxy) benzoyl) oxy] -3- Propoxyphenyl} prop-2-enoyl] propanediol

2- (3,5-diaminophenyl) -1,3 di [(2E) -3- {4 - [(4- (4,4,5,5,5- pentafluorophenoxy) benzoyl) oxy] -3-methoxyphenyl} prop-2-enoyl] propanediol

3- (4 - [(4- (1,1,2,2-tetrafluoroethoxy) benzoyl) oxy] -3 -Methoxyphenyl} prop-2-enoyl] propanediol

Benzoyl] oxy} -3 (3H) -dihydroxy-3- (4-methoxyphenyl) -Methoxyphenyl} prop-2-enoyl] propanediol

2- (3,5-diaminophenyl) -1,3 di [(2E) -3- {4 - [(4-trifluoromethoxyphenoxy) carbonyl] phenyl} prop- Dior

2- (3,5-diaminophenyl) -1,3 di [(2E) 3- {4- [(4- (2,2,2- trifluoroethoxy) phenoxy) carbonyl] phenyl} Prop-2-enoyl] propanediol

Phenyl] -1,3 di [(2E) -3- {4- [4- (4,4,4-trifluorobutoxy) phenoxy) carbonyl] phenyl} Prop-2-enoyl] propanediol

Phenyl) -1,3 di [(2E) -3- {4 - [(4- (5,5,5-trifluoropentyloxy) phenoxy) carbonyl] phenyl} Prop-2-enoyl] propanediol

2- (3,5-diaminophenyl) -1,3 di [(2E) -3- {4- [4- (4,4,5,5,5- pentafluorophenoxy) phenoxy) Yl] phenyl} prop-2-enoyl] propanediol

2- (3,5-diaminophenyl) -1,3 di [(2E) 3- {4 - [(4- (1,1,2,2-tetrafluoroethoxy) phenoxy) carbonyl] Phenyl} prop-2-enoyl] propanediol.

The diamine compound may be prepared according to methods known in the art or may be prepared by contacting a compound of formula (XIV), preferably a compound of formula (XV), with a dinitro compound of formula (XVI) And converting the nitro compound to the corresponding diamino compound of formula (XII).

_{Where, F, x 1, n 1} , n, B, D, X, Y, Z 1, L, u 1, u 2 , and S has the same meaning and preferences as given above, D1 is D as provided above With the proviso that the two amino groups of D are replaced by two nitro groups.

The reaction of compounds (XIV) and (XVI) can be carried out by a number of known methods (see J. March, Advanced Organic Chemistry, second edition, pages 363 and 365).

Generally, the process for preparing the photopolymerizable polymers of the present invention comprises the polycondensation reaction of one or more tetracarboxylic anhydrides with a diamine (I), preferably in the presence of one or more further other diamines, It is applied through a polycondensation reaction.

Preferably, the tetracarboxylic acid anhydride is a compound of formula (V).

here,

T is a tetravalent organic radical.

The tetravalent organic radical T is preferably derived from an aliphatic, alicyclic or aromatic tetracarboxylic dianhydride.

Preferred examples of aliphatic or alicyclic tetracarboxylic acid dianhydrides include:

1,1,4,4-butanetetracarboxylic acid dianhydride,

Ethylene maleic anhydride,

1,2,3,4-cyclobutane tetracarboxylic acid dianhydride,

1,2,3,4-cyclopentanetetracarboxylic acid dianhydride,

2,3,5-tricarboxycyclopentyl acetic acid dianhydride,

3,5,6-tricarboxy novinylacetic acid dianhydride,

2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride,

rel- [lS, 5R, 6R] -3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran 2', 5'-

4- (2,5-dioxotetrahydrofuran-3-yl) tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride,

5- (2,5-dioxotetrahydrofuran-3-yl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride,

Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride,

Bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid dianhydride,

1,8-dimethylbicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride,

Pyromellitic dianhydride,

3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride,

4,4'-oxydiphthalic dianhydride,

3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride,

1,4,5,8-naphthalenetetracarboxylic acid dianhydride,

2,3,6,7-naphthalenetetracarboxylic acid dianhydride,

3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride,

3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride,

1,2,3,4-furan tetracarboxylic acid dianhydride,

4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride,

4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride,

4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride,

3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride,

Ethylene glycol bis (trimellitic acid) dianhydride,

4,4 '- (1,4-phenylene) bis (phthalic acid) dianhydride,

4,4 '- (1,3-phenylene) bis (phthalic acid) dianhydride,

4,4 '- (hexafluoroisopropylidene) diphthalic acid dianhydride,

4,4'-oxyd (1,4-phenylene) bis (phthalic acid) dianhydride, and

4,4'-methylene di (1,4-phenylene) bis (phthalic acid) dianhydride.

Preferred examples of the aromatic tetracarboxylic acid dianhydride are as follows:

Pyromellitic dianhydride,

3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride,

4,4'-oxydiphthalic dianhydride,

3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride,

1,4,5,8-naphthalenetetracarboxylic acid dianhydride,

2,3,6,7-naphthalenetetracarboxylic acid dianhydride,

3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride,

3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride,

1,2,3,4-furan tetracarboxylic acid dianhydride,

4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride,

4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride,

4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride,

3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride,

Ethylene glycol bis (trimellitic acid) dianhydride,

4,4 '- (1,4-phenylene) bis (phthalic acid) dianhydride,

4,4 '- (1,3-phenylene) bis (phthalic acid) dianhydride,

4,4 '- (hexafluoroisopropylidene) diphthalic acid dianhydride,

4,4'-oxydi (1,4-phenylene) bis (phthalic acid) dianhydride,

4,4'-methylene di (1,4-phenylene) bis (phthalic acid) dianhydride,

Etc.

More preferably, the tetracarboxylic acid dianhydride used in the formation of the tetravalent organic radical T is selected from:

1,2,3,4-cyclobutane tetracarboxylic acid dianhydride,

1,2,3,4-cyclopentanetetracarboxylic acid dianhydride,

2,3,5-tricarboxycyclopentyl acetic acid dianhydride,

5- (2,5-dioxotetrahydrofuran-3-yl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride,

4- (2,5-dioxotetrahydrofuran-3-yl) tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride,

4,4 '- (hexafluoroisopropylidene) diphthalic acid dianhydride and

Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride.

Polymers, copolymers or oligomers, especially polyamic acids, polyamic acid esters and polyimides and mixtures thereof can be prepared according to known methods, for example in Plast. Eng. 36 (1996), (Polyimides, fundamentals and applications), Marcel Dekker, Inc.).

For example, the amidation and polycondensation reaction for the production of polyamic acid is carried out in the presence of a polar aprotic organic solvent such as? -Butyrolactone, N, N-dimethylacetamide, 2-butoxyethanol (BC) N-methylpyrrolidone or N, N-dimethylformamide. In most cases, equimolar amounts of anhydride and diamine, i.e., one amino group per anhydride group, are used. If it is desired to stabilize the molecular weight of the polymer, copolymer or oligomer, for that purpose, one of the two components may be added in an amount less than or in excess of the stoichiometric amount, or in a dicarboxylic monohydrate form or monoamine form, Can be added. Examples of monofunctional compounds include maleic anhydride, phthalic anhydride, aniline, and the like. Preferably the reaction is carried out at a temperature less than 100 < 0 > C.

The imidization and cyclization of the polyamic acid for the formation of polyimide can be carried out by heating, i.e. by condensation due to the removal of water or by other imidization reactions using appropriate reagents.

Partial imidation is achieved, for example, when the imidization is carried out entirely by heat, and the imidization of the polyamic acid can not always be completed, i.e. the resulting polyimide may still contain the polyamic acid moiety. The complete imidization reaction is carried out at a temperature of from 60 to 250 캜, preferably at a temperature of less than 200 캜.

To achieve imidization at low temperature, additional reagents that promote the removal of water are added to the reaction mixture. Such reagents include, for example, acid anhydrides such as acetic anhydride, propionic anhydride, phthalic anhydride, trifluoroacetic anhydride or tertiary amines such as triethylamine, trimethylamine, tributylamine, pyridine, N , N-dimethylaniline, lutidine, collidine and the like. The amount of the above-mentioned additional reagent which promotes the removal of water is preferably at least 4 equivalents of acid anhydride and 2 equivalents of amine per equivalent of polycondensation product.

The degree of imidization of each polymer used in the liquid crystal alignment agent of the present invention can be arbitrarily controlled by controlling the amount of catalyst, the reaction time, and the reaction temperature used in the production of the polymer. As used herein, the "degree of imidization" of a polymer refers to the ratio (%) of the number of repeating units of the polymer forming the imide ring or the isomeric ring to the total number of recurring units of the polymer. In the present specification, the degree of imidization of the polyamic acid not dehydrated and closed is 0%. The degree of imidization of each polymer is determined by dissolving the polymer in deuterated dimethyl sulfoxide and measuring tetramethylsilane as a standard material at room temperature by ¹ H-NMR and calculating from the following equation.

Imidization degree (%) = 1- (A ¹ / A ² B) × 100

A ¹ : Peak area based on proton of NH group (near 10 ppm)

A ² : peak area based on one proton of the acrylate double bond (near 6.5 ppm)

B: the ratio of the number of acrylate protons to one proton of the NH group in the polymer precursor

Is generally in the range of 1 to 99%, preferably 5 to 50%, more preferably 10 to 40%, imidized.

The cyclization can be carried out after the polycondensation reaction together with the removal of water from the water during the formation of the polyimide.

A further preferred embodiment of the invention relates to a photo-alignment polymer comprising photoreactive groups which are coumarin- and quinoline-groups as described, for example, in US 6,201, 081 B1, which is incorporated by reference. US 6,201,087, those described in claims 1-14; More preferably, in Examples 1-10, Column 10, Line 6 to Column 31, Line 54 are listed.

A further preferred embodiment of the invention relates to a photo-aligned polymer comprising a cyano stilbene-group photoreactive group as described, for example, in US 7959990.

More preferred are photo-alignment polymers comprising at least one monomer of formula (IV) or at least two monomers.

here,

A and B are each independently a ring system of 5 to 40 atoms wherein each ring system is linked via an electron conjugation (pi-pi bond) to at least two Including one unsaturation,

Wherein the ring system is selected from the group consisting of halogen atoms, hydroxyl groups and / or polar groups such as nitro, nitrile or carboxy groups, and / or cyclic, straight or branched chain alkyl residues of 1 to 30 carbon atoms, and / or is optionally substituted by chlorine-substituted, or is unsubstituted or substituted by a) one may be substituted or multiply substituted, wherein one or more, preferably non-adjacent -CH ₂ - groups are independently selected from -O -, -CO-CO-O-, -O-CO-, -NR ¹ -, -NR ¹ -CO-, -CO-NR ¹ -, -NR ¹ -CO- ^{NR 1 -, -NR 1 -CO-} NR 1 -, -CH = CH-, -C≡C-, -O-CO-O- and _{-Si (CH 3) 2 -O-} Si (CH 3) 2 -, aromatic or alicyclic group, wherein R ¹ is a hydrogen atom or is selected from the group consisting of lower alkyl; And / or an acryloyloxy, alkoxy, alkylcarbonyloxy, alkyloxycarbonyloxy, methacryloyloxy, vinyl, allyl, vinyloxy and / or allyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms Oxy group,

S ¹ is a single covalent bond or a spacer unit;

n is 1, 2 or 3;

X and Y are each a hydrogen atom and the other is preferably a group -COR ² , -COOR ² , -COSR ² , -CO-NR ² , -SOR ² , -SOCF ₃ , -SO ₂ CF ₂ COR ² , -SOOR ² , -C≡S, -NO ₂ , -CF ₃ , -CN, wherein R ² is a hydrogen atom, a straight or branched chain alkyl of 1 to 16 carbon atoms or an alkyl Wherein one or more, preferably not adjacent, -CH ₂ - groups are independently selected from the group consisting of -O-, -CO-, -CO-O-, -O-CO-, -C = C-, -C Lt; RTI ID = 0.0 > C-group, < / RTI > or by optionally substituted alkyl,

G is a hydrogen atom optionally substituted with alkyl or is a polymerizable group,

However, Y is -CN and A is unsubstituted phenylene, B is -CN, -NO ₂ or -COOH by a para-substituted phenyl can not renil;

With the proviso that when ring system A is unsubstituted or substituted with halogen, cyano and / or nitro and ring system B is unsubstituted or substituted with halogen, cyano and / or nitro, X is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, -CN and -COO-alkyl having 1 to 12 carbon atoms.

A further preferred aspect of the present invention is

- J. < / RTI > Photopolym. Sci. Technol., 11, 187 (1998), Chem. Mat., 11, 1293 (1999)],

- Macromol. Chem. Phys., 199, 375 (1998)], benzylidene phthalimidine,

- Literature [Japan. J. Appl. Phys., 1, 37, 2620 (1998)],

- J. < / RTI > Photopolym. Sci. Technol., 12, 279 (1999)],

- an azo derivative group described in Chemical Reviews, 100, 1847 (2000)

, Which are incorporated herein by reference.

Particularly most preferably, the present invention, within the meaning and preferences described above and below,

(a) at least one diamine (I) or at least one diamine (I) and at least one tetracarboxylic dianhydride having a photoreactive group which is a polyamic acid, a polyimide or a mixture thereof, preferably a polyamic acid At least one single < RTI ID = 0.0 >

≪ / RTI >

Further particularly, and most preferably, the present invention, within the meaning and preference described above,

c) a further polymer not having photoreactive groups, which is a polyamic acid, a polyimide or a mixture thereof, comprising at least one diamine (DX) and at least one tetracarboxylic dianhydride

≪ / RTI >

In general, the amount of photo-alignment polymer is from 0.5 to 50% by weight, preferably from 1 to 25% by weight, most preferably from 1 to 20% by weight, especially from 1 to 20% by weight, based on the total weight of the polymer having no photo- Preferably 1 to 15% by weight, more particularly most preferably 1 to 10% by weight.

In the context of the present invention, the diamine (DX) has the meaning of an organic diamine. The diamine (DX) is commercially available or may be accessible by known methods. The secondary amino group is accessible by, for example, a substitution reaction. Preferably, the diamine (DX) is selected from the group of the following compounds:

here,

L, L _1, L ₂ and L ₃ are independently _{hydrogen, -CH 3, -COCH 3, -OCH} 3, nitro, nitrile, halogen, CH ₂ = CH-, CH ₂ each = C (CH ₃₎ -, _{CH 2 = CH- (CO) O-} , CH 2 = CH-O-, -NR 5 R 6, CH 2 = C (CH 3) - (CO) O- or _{CH 2 = C (CH 3)} -O -ego,

T, T ₁ , T ₂ and T ₃ independently of one another are hydrogen, substituted or unsubstituted straight or branched C ₁ -C ₂₄ alkylene groups, in which one or more C-atoms, CH- or CH ₂ - Independently of one another, can be replaced by a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, and / or by a heteroatom and / or by a linking group;

u ₃ , u _{3 '} and u _{3 "} are independently of each other an integer from 0 to 2;

R ⁵ and R ⁶ each independently represent a hydrogen atom or C ₁ -C ₆ alkyl;

Z ⁴ represents a substituted or unsubstituted, straight or branched C ₁ -C ₂₀ alkylene group, wherein one or more -CH ₂ - groups are independently of each other a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or hetero By a cyclic group and / or by a heteroatom and / or by a bridging group; Preferably Z ⁴ is an unsubstituted or substituted straight or branched C ₁ -C ₁₂ alkylene group, C ₁ -C ₆ alkylene, wherein one or more, preferably not adjacent, -C-atoms, CH- Or the CH ₂ - group may be replaced by an oxygen or nitrogen atom; More preferably Z ⁴ is methylene, ethylene, propylene, 2,2-propylene, butylene, pentylene, hexylene, (-OC ₁ -C ₆ alkylene) or _two methylene (- (CO) O- C ₁ -C ₆ alkylene) ₂ methylene or mono- or bi-radical thereof;

The diamine (DX) is the following compound:

Wherein X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ and X ¹¹ are independently of each other a bridging group or a single bond; Preferably X ⁷ and X ⁸ , X ⁹ and X ¹⁰ or X ¹¹ independently of one another are a single bond, -O-alkoxy-, for example -O-methylene-, methylene-O-; C ₁ -C ₁₂ alkylene such as methylene, ethylene, propylene, butylene, pentylene or hexylene, substituted or unsubstituted 1,1'-cyclohexylene, -SO-, -S-, -SO _{2 -, -O-, -N (R} 25) -, -C (CH 3) 2 -, -C (CF 3) 2 -, 1,1'- cyclohexyl, which is optionally substituted 4- (C ₁ -C ₃₀ alkyl) - cyclohexyl, substituted or unsubstituted 3, 4 "- bis _{[4 '- (C 1 -C} 30 alkyl) -1,1' non-(cyclohexyl) -4-yl], 1, 1 ' -bicyclohexyl) -4-yl, wherein ^R25 is hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl;

Preferably X ¹⁰ is _{-SO-, -SO 2 -, -O-,} -N (CH 3) -, -C (CH 3) 2 -, -C (CF 3) 2 -, 1,1'- Cyclohexyl, 4- (C ₁ -C ₃₀ alkyl) -cyclohexyl, 3,4 "-bis [4 '- (C ₁ -C ₃₀ alkyl) -1,1'- X ⁹ and X ¹¹ are the same and are methylene, ethylene, propylene, butylene, pentylene, hexylene, a single bond or -O-;

n is an integer from 0 to 3, preferably 0 or 1;

When n is 0, X ⁹ and X ¹¹ are the same and are the same or different from each other, such as methylene, ethylene, propylene, butylene, pentylene, hexylene, single bond -O-; -S-, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -;

The diamine (DX)

이고,

ego,

Wherein X ⁵ is a bridging group or a single bond and X ¹⁷ is CH ₂ , O, NH;

The diamine (DX) is of the formula (XV)

Wherein R ⁹ , R ¹⁰ and R ¹¹ are hydrogen or C ₁ -C ₃₀ alkyl, preferably R ⁹ and R ¹⁰ are hydrogen, methyl and R ¹¹ is hydrogen or C ₁ -C ₃₀ alkyl, is methyl, or a 2-methyl-heptane, n is 0, y is 1 and y is 0, and when n is 1, y1 is a single bond or a double bond, X ¹⁸ is a carbonyl group or a single bond or NH , X ¹⁷ is CH ₂ , O, NH;

The diamine (DX)

이고,

ego,

More preferably,

이고,

ego,

Wherein R ¹¹ and R ¹² are hydrogen or C ₁ -C ₃₀ alkyl, preferably methyl,

X ¹⁵ and X ¹⁶ are independently of each other a single bond or C ₁ -C ₃₀ alkyl, preferably C ₁ -C ₆ alkyl, -COO- and -CONH-; -COO (C ₁ -C ₆ alkylene) -, -CONH (C ₁ -C ₆ alkylene) -.

More preferred diamines (DX) of formula (IX-1) are:

Wherein X ⁶ is a bridging group or a single bond and is preferably, for example, -O-, -S- or optionally substituted, branched or straight chain C ₁ -C ₆ alkylene, -O (CH ₂ CH ₂ O) _n -; -O- (C ₁ -C ₁₂ alkyl) _n -O-, -S- (C ₁ -C ₁₂ alkyl) _n -S-, triazine, 1,3,5- tree-one, _{^{1,1'-cyclohexylene, NR 5 ((C 1 -C}} 6 alkyl) _n NR ^6), - (piperidine) _n1 - (C ₁ -C ₆ alkyl) _n - (piperidin- ) _n ,

Here, n is an integer of 1 to 6, n1 is an integer of 0 to 6,

R ⁵ and R ⁶ each independently represent a hydrogen atom or C ₁ -C ₆ alkyl;

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently of the other hydrogen or C ₁ -C ₃₀ alkyl, preferably methyl; X ⁶ is a single bond, -O-, or -CH ₂ -;

Particularly preferred diamines (DX) are selected from the following compounds:

And

Wherein n is independently 0 or 1;

R ³ is C ₁ -C ₂₄ alkyl, preferably at least one C ₁ -C ₆ alkyl, more preferably methyl, ethyl, propyl;

R ⁹ and R ¹⁰ are independently of each other hydrogen or C ₁ -C ₃₀ alkyl, preferably R ⁹ and R ¹⁰ are independently of each other hydrogen or methyl, and R ¹¹ and R ¹² are each independently of the other hydrogen or C ₁ -C ₃₀ alkyl, preferably methyl;

X ¹⁴ and X ¹⁷ are, independently of each other, a bridging group or a single bond and are preferably, for example, -O-, -S- or substituted or unsubstituted, branched or straight chain C ₁ -C ₆ alkylene, - _{O (CH 2 CH 2 O)} n -; -O- (C ₁ -C ₁₂ alkyl) _n -O-, -S- (C ₁ -C ₁₂ alkyl) _n -S-, triazine, 1,3,5- tree-one, _{^{1,1'-cyclohexylene, NR 5 ((C 1 -C}} 6 alkyl) _n NR ^6), - (piperidine) _n1 - (C ₁ -C ₆ alkyl) _n - (piperidin- ) _n ,

n is an integer of 1 to 6, n1 is an integer of 0 to 6,

R ⁵ and R ⁶ each independently represent a hydrogen atom or C ₁ -C ₆ alkyl;

A further more preferred diamine (DX) is

4,4'-diaminodiphenyl, 4,4'-diaminodiphenyl-3,3'-dimethoxy, 4,4'-diaminodiphenyl-3,3'-dimethyl, Diaminodiphenylsulfone, 4,4'-diamino-diphenylsulfone, 4,4'-diamino-diphenylsulfone, 4,4'-diamino-diphenylsulfone, Diaminodiphenyl-bis (trifluoromethyl) -methylene, 4'-diamino diphenylcarbonyl, 4,4'-diaminodiphenyloxomethylene, 4,4'-diaminodiphenyl- Bis (trifluoromethyl) methylene-3,3'-dihydroxy, 4,4'-diaminodiphenyl-bis (trifluoromethyl) methylene- Bis [4- (4-aminophenoxy) phenyl] -hexafluoro-propane, 4,4'-diaminodiphenyl ether, Bis [4,4-amino-2-trifluoromethyl-phenoxy) phenyl) hexafluoropropane, 4,4'-diamino-2,2'-bis / trifluoromethyl ) -Biphenyl, 4,4'-bis [4-amino-2-trifluoromethyl Yl) phenoxy] -octafluorobiphenyl;

In addition, the diamine (DX) is as provided below:

Wherein n is 0 or 1, X ⁹ and X ¹⁰ or X ¹¹ have the meanings and preferences given above;

And further, 1-cholesteryl-oxy-2,4-diamino-benzene, 1-cholestanyloxy-2,4-diaminobenzene, cholestearyloxy (3,5-diamino-benzoyl) , Cholestan-yloxy (3,5-diaminobenzoyl);

In addition, the diamine (DX) is the diamine described in page 10, line 48-58 and page 11, line 1-19 of EP-A-1,818,354, which is incorporated by reference.

The diamine (DX) of formula (IX-1) is most preferred.

Wherein X ⁶ has the meanings and preferences given above and is preferably, for example, a single bond, -O-, -S- or substituted or unsubstituted C ₁ -C ₆ alkylene, -O- (CH ₂ CH ₂ O) _n -; -O- (C ₁ -C ₁₂ alkyl) _n -O-, -S- (C ₁ -C ₁₂ alkyl) _n -S-, triazine, 1,3,5- tree-one, _{^{1,1'-cyclohexylene, NR 5 ((C 1 -C}} 6 alkyl) _n NR ^6), - (piperidine) _n1 - (C ₁ -C ₆ alkyl) _n - (piperidin- ) _n ,

Here, n is an integer from 1 to 6, n1 is an integer from 0 to ^{6, R 11, R 12,} R 13 and R ¹⁴ each independently has the same meaning and preferences provided above each other, preferably X ⁶ is a single bond, -O-, -CH ₂ -.

Further most preferred diamines (DX) are as provided below:

Wherein X ⁶ , R ¹¹ and R ¹² independently of one another have the same meaning and preference as given above and R ¹¹ and R ¹² are preferably hydrogen, C ₁ -C ₆ alkyl, preferably C ₁ -alkyl or and hydroxyl, X ⁶ is preferably a single bond, -O-, -CH ₂ - a.

In the intended application method, it may be advantageous to adjust the composition by adding additional solvent. Thus, the invention also relates to a photo-alignment composition within the provided substrate and preferences, which also comprises d) at least one further solvent.

The term "additional solvent" in the context of the present invention has the following meanings and preferences:

The solvent or solvent mixture used in the present invention may be any solvent capable of dissolving the composition according to the present invention. Preferably the at least one further solvent is a polar solvent or a non-polar solvent. Particularly preferred solvents are those which result in excellent coating or printing ability of the photo-alignment composition for substrates such as glass.

Nonpolar solvents have low dielectric constants and are not miscible with water, such as hexane, benzene, toluene, diethyl ether, chloroform, ethyl acetate, dichloromethane, chlorobenzene.

Preferred polar solvents are aprotic or protic polar polar solvents.

Polar aprotic solvents share ionic dissolving power with protic solvents, but acidic hydrogen is a poor solvent. These solvents generally have a high dielectric constant and are highly polar. Examples are 1,4-dioxane, tetrahydrofuran (THF), acetone, acetonitrile (MeCN), N, N-dimethylformamide (DMF), N, N-dimethylacetamide, dimethylsulfoxide (DMSO) N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N-vinylpyrrolidone, tetramethylurea, hexamethylphosphoric triamide, gamma-butyrolactone (BL) (MEK), ethyl acetate (EA), or a mixture of two or more kinds of solvents selected from the group consisting of acetone, methyl ethyl ketone, methyl ethyl ketone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, Methoxy-2-propanol acetate (MPA), diethyleneglycol diethyl ether, dichloromethane, dichloromethane, chloroform, acetonitrile, And mixtures thereof. Preferred aprotic solvents include N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), diethylene glycol diethyl ether, ethyl ethoxypropionate or gamma-butyrolactone (BL) And mixtures thereof. N-methylpyrrolidone (NMP) is particularly preferred.

A polar protic solvent is a solvent containing dissociable H < + >, for example hydrogen fluoride, and is referred to as a protic solvent. The molecule of the solvent can donate H + (proton). On the other hand, aprotic solvents can not donate hydrogen bonds. A common characteristic of protic solvents is that they exhibit hydrogen bonding, that they have acidic hydrogen (which is very weakly acidic), that they stabilize ions (cations by free unpaired atoms, anions by hydrogen bonding) It is possible. Examples are acetic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, formic acid, 2-butoxyethanol (BC), ethylcarbitol, butylcarbitol, ethylene glycol, propylene glycol monoacetate, dipropylene glycol monomethyl Ether and water. A preferred polar protic solvent is 2-butoxyethanol (BC).

Preferred additional solvents are gamma-butyrolactone (BL), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), 2-butoxyethanol (BC), diethylene glycol diethyl ether, N, N-dimethylacetamide, N, N-dimethylformamide, ethylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol , Propylene glycol monoacetate, propylene glycol diacetate, dipropylene glycol and dipropylene glycol monomethyl ether, chlorobenzene, tetrahydrofuran, N-methylpyrrolidone (NMP), butyl cellosolve, cyclopentanone ), Methyl ethyl ketone (MEK), ethyl acetate (EA), anisole (AN), cyclohexanone (CHN), methyl isobutyl ketone (MIBK), 1-methoxy- , N-dimethylformamide (DMF), dichloromethane, gamma-butyrolactone (BL), and mixtures thereof.

More preferred solvents include but are not limited to gamma-butyrolactone (BL), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N-vinylpyrrolidone, (CH 3) 2-butoxyethanol (BC) butyl cell (N-dimethylformamide), N-dimethylformamide, ethyl cellosolve, methyl ethyl ketone (MEK), diethylene glycol diethyl ether, ethyl ethoxypropionate, cyclohexanone Propyleneglycol monoacetate, propyleneglycol diacetate, dipropyleneglycol, and dipropyleneglycol monomethylether, chlorobenzene, tetrahydrofuran, and the like, and those selected from the group consisting of ethylenediaminetetraacetate, ethyleneglycol monomethylether, ≪ / RTI >

Most preferred additional solvents are methyl ethyl ketone (MEK), cyclohexanone (CHN), butyrolactone (BL), N-methylpyrrolidone (NMP), diethylene glycol diethyl ether, ethyl ethoxypropionate , N-ethylpyrrolidone (NEP), dimethylformamide and 2-butoxyethanol (BC), and mixtures thereof.

(NMP), N-ethylpyrrolidone (NEP), diethylene glycol diethyl ether, ethyl ethoxypropionate, dimethylformamide and / or 2- (BC) is most particularly preferred and N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), dimethylformamide and / or 2-butoxyethanol More particularly, it is most preferable.

A further aspect of the invention is that within the meaning and preference given above, in addition to at least one aprotic polar solvent, preferably two aprotic polar solvents, more preferably N-methylpyrrolidone (NMP) Methylpyrrolidone (NMP) and 2-butoxyethanol (BC) or N-ethylpyrrolidone (NEP), preferably at least one solvent selected from N-ethylpyrrolidone (NEP) And 2 aprotic solvents such as 2-butoxyethanol (BC).

A more preferred embodiment of the present invention is that within the above-mentioned meanings and preferences, preferably in the range of 1 to 100 mPa.s, more preferably in the range of 1 to 50 mPa.s, even more preferably in the range of 10 to 40 mPa.s Range (for offset printing), in the range of 4 to 15 mPa.s (for inkjet printing), most preferably in the range of 15 to 40 mPa.s (for offset printing); And a viscosity in the range of 4 to 10 mPa.s (for ink jet printing) to a substrate, wherein the composition comprises butyrolactone ( At least one solvent selected from the group of solvents such as N-methylpyrrolidone (BL), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), dimethylformamide and 2-butoxyethanol , And the amount of the solvent (I) and any additional solvent in the composition of the present invention is in the range of 99 to 70% by weight, preferably 99 to 80% by weight, more preferably 99 to 90% by weight.

The sum of all weight ratios of all components comprising the solvent of the photo-alignment composition of the present invention is 100%.

In the present invention, the photo-alignment composition of the present invention may further comprise a surfactant.

Surfactants are chemicals that physically adsorb at the surface or interface and tend to change the energy relationship at the interface. This causes the surfactant to change the surface tension.

Suitable surfactants include wetting, or leveling-, blocking-, scratch-, slip-, mar- or abrasion- resistant-; Degassing-, vesicle-, hydrophobing-, dispersing-, rheology control- formulation; Preferably wetting, leveling, blocking-scratching, slip-, wear- or wear-resistant-formulations; Dispersion-and rheology control-formulations; More preferably wetting, dispersing, leveling, blocking-scratch-resistant-formulations; Most preferably a wetting, dispersing, and leveling-agent. Wet-and leveling-formulations are particularly preferred.

Surfactants having the aforementioned properties are well known in the art.

Preferably, the surfactant is non-polymeric or polymeric; Reactive or non-reactive, saturated or unsaturated; Nonionic, amphoteric, anionic or cationic compounds. In the context of the present invention, the reactivity has the meaning of crosslinkable, polymerizable, or dimerizable.

Preferred surfactants are polymeric and are capable of cross-linking, polymerizing, or dimerizing.

Amphoteric is, for example, alkyl ampho (di) acetate, amidobetaine or alkaline betaine.

The cationic surfactants are, for example, alkyldimethylamine, alkylamidopropylamine, alkylimidazoline derivatives, quaternized amine ethoxylates, quaternary ammonium compounds;

More preferably, the surfactant, which is a polymer, is a homopolymer or copolymer (block, statistical, graphical, branched) or is a reactive or non-reactive, for example, a crosslinkable, polymeric, or dimerizable surfactant. Reactive, for example, crosslinkable surfactants are most preferred.

Examples of non-polymeric surfactants are organic sulfonate derivatives such as alkylphenol ether sulfates, alpha olefin sulfonates, aromatic hydrocarbon sulfonic acids, salts and blends, naphthalene sulfonates, condensed naphthalene sulfonates, fatty acid alcohol sulfates Mono-alkylsulfosuccinates, alkylsulfosuccinamates, di-alkylsulfosuccinates, lecithin derivatives such as sojalecitine; di-alkyl sulfosuccinates; Tenside derivatives such as cationic, anionic or amphoteric surfactants, especially fatty acid ester derivatives; Carboxylic acid esters or ether derivatives, such as hydroxy-functional carboxylic acid esters or ether derivatives, alkyl ether phosphates, alkyl ether carboxylic acids and salts, alkyl ether sulfates; Alkylbenzenesulfonic acid and salts, alkylphenol ether phosphates, alkylphenol ether sulfates, aromatic hydrocarbonsulfonic acids, salts and blends.

Preferred non-polymeric surfactants are carboxylic acid esters or ether derivatives, in particular Disperbyk®-108.

Examples of polymeric surfactants are, for example, organic polymers such as amide polymers, imide polymers, polyurethanes, silicone / siloxane polymers, fluoropolymers or acrylate polymers, polyether polycarboxylic acid structures Polysiloxane or amine derivative), or a nonionic dispersion polymer.

Organic polymer is a surfactant, for example, the hydrocarbon surfactant, for example a high boiling point aromatic solvent, ketone and ester blend, or fame (F atty A cid M odified E mulsifiers) (fatty acid modified emulsifier).

Fame is based on fatty acid chemistry and has a polar head based on a quaternary amine, such as fatty acid modified polyesters, aliphatic polyethers having acidic groups, fatty acid modified solutions, and polyesters in water.

Silicone / siloxane polymers include, for example, reactive or non-reactive polysiloxanes,

Organically modified polysiloxane

Organically modified polysiloxane

The fluorocarbon-modified polysiloxane

No solvent-modified polysiloxane

Modified polysiloxane emulsion

Polysiloxane

The polysiloxane copolymer

The polyether siloxane copolymer

Isocyanate-terminated polysiloxane

Polysiloxanes modified with unsaturated end groups

Polysiloxane modified polyisocyanate

Emulsion of polyether siloxane copolymer

The polysiloxane-based product containing fumed silica

Silicone acrylate.

Fluoropolymers include, for example,

The fluorocarbon-modified polymer

Fluorocarbon modified polyacrylates

Fluorosilicone

Polymeric fluorocarbon compound.

The acrylate polymer may be, for example,

Acrylic polymer

Ammonium polyacrylate

Sodium polyacrylate

Ammonium polyacrylate copolymer

Sodium polyacrylate copolymer.

The nonionic dispersion polymer may be, for example,

Amine oxide

Alkylpolysaccharide

Block copolymer

Castor oil ethoxylate

Ceto-oleyl alcohol ethoxylate

Cetostearyl alcohol ethoxylate

Decyl alcohol ethoxylate

Dinonyl phenol ethoxylate

Dodecylphenol ethoxylate

End-capped ethoxylate < RTI ID = 0.0 >

Ether amine derivative

Ethoxylated alkanolamide

Ethylene glycol ester

Fatty acid alkanolamide

Fatty acid alcohol alkoxylate

Lauryl alcohol ethoxylate

Mono-branched alcohol ethoxylate

Neutral alcohol ethoxylate

Monylphenol ethoxylate

Octylphenol ethoxylate

Oleylamineethoxylate

Random copolymer alkoxylate

Sorbitan ester ethoxylate

Stearic acid ethoxylate

Stearylamine ethoxylate

Synthetic alcohol ethoxylate

Tall oil fatty acid ethoxylate

Tallow amine ethoxylate

Trid tridecanol ethoxylate. ≪ / RTI >

Preferred polymeric surfactants are nonionic polymeric surfactants, especially silicone or siloxane polymers, and most preferably silicone acrylates, especially Tego Rad 2500.

A further preferred embodiment of the invention relates to compositions of two or more surfactants.

Typical suppliers for surfactants with wettability and leveling properties include ADD APT, Air Products, Akzo-Nobel, Akzo-Nobel Cellulosic Specialties, BASF, Borchers, BYK Chemie, Ciba Specialty Chemicals, Cognis, Condea Servo, Dow Chemical, Dow Chemical, Dow Corning, DuPont, GE Silicones, International Specialty Products, Rhodia, Tego, Tiarco Chemical, Troy, UCB Chemical, Ultra Additive, Worlee, 3M, Additek, CP Hall, Cytec, Efka Additives, Hercules, Liaoyang Huaxing Chemical, Polyvel, RT Vanderbilt, Sovereign Chemical, Stepan, Tiarco Chemical, Sachtleben, Rhodia, Raschig and Potters Ballotini.

Examples of surfactants having wettability and leveling properties are as follows:

- Available from Tego / Degussa: Tego® Colorol, Tego® Dispers, Tego® Lipotin, Tego® Twin, Tego® Wet, Rewopol®, Tego® Surten, Tego®Rad, Tego® Glide, Tegomer®, Tego® Dispers 662 C, Tego® Dispers 662 C, Tego® Dispers 680 UV, Tego® Dispers 660 C, Tego® Dispers 661 C, Tego® Dispers 662 C, Tego® Colorol E, Tego® Colorol E, Tego® Wet 260, Tego® Wet 265, Tego® Wet 270, Tego® Wet 250, Tego® Wet 260, Tego® Wet 265, Tego® Lipotin DB, Tego® Lipotin DB, Tego® Lipotin SB, , Tego® Wet 280, Tego® Wet 500, Tego® Wet 505, Tego® Wet 510, Tego® Wet 590, Tego® Wet 591, Tego® Wet KL 245, Rewopol® B 2003, Rewopol® M 365, Tego® Surten W 125, Tego® Surten W 130, Rewopol® SB DO, Rewopol® SB DO 75, Rewopol® SB DO 75, Rewopol® SB FA 50, Rewoquat® W 75, Rewoteric® AM CAS, Tego® Surten W 133, Tego® Surten W 5840, Tego® Surten W 5878, Tego® Rad 2100, Tego® Rad 2200 N, Tego® Rad 225 0, Tego® Rad 2300, Tego® Rad 2500, Tego® Rad 2600, Tego® Rad 2700, Tego® Glide 130, Tego® Glide 406, Tego® Glide 410, Tego® Glide 411, Tego® Glide 415, Tego® Glide 420, Tego® Glide 432, Tego® Glide 435, Tego® Glide 440, Tego® Glide 450, Tego® Glide 482, Tego® Glide 115, Tego® Glide B 1484, Tego® Glide ZG 400, Tegomer® CSi 2342, Tegomer® D 3403, Tegomer® E-si. Tegomer® ESi 2330, Tegomer® HSi 2311, Tegomer® VSi 2250.

Available from Efka: EFKA 3033, EFKA 3034, EFKA 3232, EFKA 3277, EFKA 3299, EFKA 3883, EFKA 6903, EFKA 6906, EFKA 3522, EFKA 5010, EFKA 5044, EFKA 5054, EFKA 5055, EFKA 5063, Efka® 3600, Efka® 3650, Efka® 3650, Efka® 4590, EFKA® 5065, EFKA® 5070, Efka® 6225, Efka® 6230, Efka®, Efka® 7311, Efka® 7335, Efka® 7316, Efka® 7340, Efka® 7361, Efka® 7375, Efka® 7381, Efka® 7390, Efka® 7500, Efka® 7544, Efka® 7554, Efka® 7564

Byk® additives such as Byk® 307, Byk® 333, Byk® 9075, Byk® 9076, Byk® 9077, Byk® 935, Byk® 961, Byk® A 560, Byk® W 909 BYKOPLAST® 1000, Disperplast 1011, Byk® S 706, Byk® W 909, Aquacer® 840, Byk®-077, Byk®-085, Byk®-315, Byk®-320, Byk®- 344, Byk®-348, Byk®-342, Byk®-346, Byk®-346, Byk®- 353, Byk-355, Byk-355, Byk-357, Byk-358 N, Byk- Byk®-365 P, Byk®-366 P, Byk®-368 P, Byk®-370, Byk®-373, Byk®-375, Byk®-UV 3500, Byk®-UV 3510, Byk®-S 706, Byk®-Silclean 3700, Byk®-380, Byk®-390, UV 3530, Byketol®-OK, Byketol®-Special, Byketol®-WS, Minerpol® 221, DisperByk®-108.

The most preferred surfactants are Tego®Flow 300, Tego®Rad 2600, Tegomer® E-si, Tego®Rad 2700, EFKA-3883, EFKA 6903, EFKA 6906, EFKA 3299, Tego® with a pigment affine group Rad 2500 polydimethylsiloxane and DisperByk®-108 hydroxyl functionalized carbonic acid ester. Particularly preferred surfactants are Tego®Flow 300, Tego® Rad 2500 and DisperByk®-108.

The term substrate, within the scope of the present invention, describes a base material on which a process is performed to create one or more layers or films on some or all of the entire surface of the base material. The substrate can be made of any type of solid material, such as, for example, glass, metal, polymeric films or composite materials. Although not necessarily, in most cases, the substrate is applied in slab-like or individually cut pieces, or in the case of a flexible base material, to a cylindrical shape.

In a further preferred embodiment, the present invention relates to a process for the production of optical fibers, which further comprises a surfactant in the solvent within the meaning and preference given above in the range from 1 to 99%, preferably from 1 to 20%, more preferably from 1 to 10% ≪ / RTI >

The amount of the surfactant in the composition is determined depending on the intended performance in terms of mechanical and thermal stability, and optical and electro-optical performance.

In a further preferred embodiment, the present invention relates to the use of a liquid crystal photo-alignment material wherein the additional level of surfactant on the liquid crystal photo alignment material is less than 20%, preferably from 0.01 to 10%, more preferably from 0.1 to 5% %. ≪ / RTI >

Preferably, the present invention relates to a photo-alignment composition further comprising a surfactant, wherein the composition has a voltage holding ratio (VHR), residual DC (RDC) or an AC memory ) (ACM).

VHR, ACM, and RDC are values that are commonly known in the liquid crystal display technology field and can be described as follows:

VHR : In the case of a thin film transistor type liquid crystal display, a certain amount of charge is applied to an electrode of a pixel over a very short time period, and then it should not be drained by the resistance of the liquid crystal. The ability to maintain the charge and thus maintain the voltage drop across the liquid crystal is quantified as a "voltage holding ratio" (VHR). This is the ratio of the root mean square voltage (RMS voltage) at one pixel within one frame period (the effective voltage) to the initial value of the applied voltage.

ACM (alternating current memory) : An AC (alternating current) voltage of 7 volts (1 kHz) is applied to the cell for 700 hours. The pretilt angle of the cell is measured before and after AC stress is applied. The ACM performance is shown in terms of the pre-tilt angle difference??.

RDC (Residual Direct Current) : Since an adjustable DC component of V = 2VDC is added to the symmetrical square wave signal of V = 2.8V (30Hz), the fluctuation of the light transmitted by the test cell is Can be removed or at least minimized by appropriate selection of external DC components. The external-DC voltage at which the flicker is removed or minimized by compensation of the internal residual DC-voltage is considered equal to the internal residual-DC voltage.

Nonionic surfactants that do not have any negative effects on voltage holding ratio (VHR), residual DC (RDC) or AC memory (ACM) are preferred.

A further preferred aspect of the present invention relates to a method of making a liquid crystal alignment layer comprising applying to the substrate a photo-alignment composition as described above, by printing or coating, by all described preferences.

In general, the composition is applied on a substrate optionally coated with an electrode (for example, a glass plate coated with indium-tin oxide (ITO)) to produce a homogeneous layer 0.05 to 100 탆 thick.

A further preferred embodiment of the present invention relates to a process as described above and to a process for producing a homogeneous liquid crystal aligned layer of zero defect < 300 nm, preferably < 250 nm, more preferably & &Lt; / RTI &gt; Preferably, the liquid crystal photo alignment material is a polymer comprising diamine (I) and tetracarboxylic acid anhydride as described above and having all of the above-mentioned preferences.

Coating methods include, for example, spin coating, air doctor coating, blade coating, knife coating, reverse roll coating, transfer roll coating, gravure roll coating, kiss roll coating, cast coating, spray coating, spin- Coating, wire-coating, slot-orifice coating, calender coating, electrodeposition coating, dip coating or die coating.

Printing methods include, for example, ink jet printing, direct printing, relief printing (e.g., flexographic printing), intaglio printing (such as direct gravure printing or offset gravure printing), lithographic printing Offset printing), or stencil printing (e.g., screen printing, flexographic-printing, or planar-printing).

Direct printing, such as gravure, flexography; Screen printing and letterpress printing processes are preferred; Indirect printing, such as offset printing; And flat printing, such as lithography; Relief printing, intaglio printing and inkjet printing; And flexographic printing are further preferred.

The description of the single printing process is conventional knowledge and is provided partially below.

A further preferred embodiment of the present invention is a process for the preparation of a compound of formula I by printing, preferably by indirect printing, for example by offset printing; Planar printing, e.g. lithography; Relief printing, intaglio printing; Ink jet printing, or flexographic printing; More preferably the composition as applied to the substrate by ink jet printing, and all described preferences of the method.

A further preferred aspect of the present invention is a method as described above and a method as described above, further comprising treating, preferably alignment, more preferably cross-linking and / or isomerizing, the liquid crystal photo- Lt; / RTI &gt;

The alignment target area is irradiated using, for example, a high-pressure mercury vapor lamp, a xenon lamp, or a pulsed UV laser, using a polarizing plate and, optionally, a mask for generating a structural image.

Further, by controlling the irradiation directions of the polarization plane and / or the alignment light, the alignment direction and the tilt angle in the liquid crystal alignment layer can be changed. It is understood that by selectively irradiating a particular region of the liquid crystal alignment layer, a very specific region of the layer can be aligned. In this way, a layer having a defined tilt angle can be provided. The induced orientation and tilt angle are maintained in the liquid crystal alignment layer by a process, in particular by a crosslinking process.

The processing of the alignment light may be performed in a single step or in several separate steps. In a preferred embodiment of the present invention, the alignment light processing is performed in a single step.

The incident direction of the alignment light may be normal to the substrate or may be an arbitrary tilt angle.

In order to generate the tilt angle, the alignment light is preferably exposed at an inclination angle.

A further preferred method of the present invention is

A method of manufacturing a vertically aligned liquid crystal alignment layer;

A method of making a multi-domain vertical alignment of a liquid crystal alignment layer;

To a method for manufacturing a liquid crystal alignment layer having a tilted optical axis

.

In addition, the present invention relates to the use of a liquid crystal alignment layer comprising a photo-alignment composition described in the present invention and made in accordance with the method of the present invention within the meaning and all preferences provided in liquid crystal alignment.

A further aspect of the invention relates to a liquid crystal alignment layer obtainable by the process of the present invention.

Preferably, the present invention relates to a liquid crystal alignment layer comprising a photo-alignment composition according to the invention in cross-linked and / or isomerized form.

A further preferred embodiment of the present invention relates to a liquid crystal alignment layer having a thickness of < 300 nm, preferably < 250 nm, more preferably < 200 nm.

The liquid crystal alignment layer can be used in the production of unstructured or structured optical or electro-optical elements, preferably in the manufacture of hybrid layer elements.

In general, a transparent support such as a glass or plastic substrate optionally coated with indium-tin oxide (ITO) is used.

In addition, by controlling the irradiation direction of the alignment light, the alignment direction and the tilt angle in the liquid crystal alignment layer can be changed. It is understood that by selectively irradiating a particular region of the polymer or oligomer layer, a very specific region of the layer can be aligned. In this way, a layer having a defined tilt angle can be provided. The induced orientation and tilt angle are maintained in the liquid crystal alignment layer by a process, in particular by a crosslinking process.

More preferably, the present invention relates to a method wherein imidization is carried out before or after applying the polymer, copolymer or oligomer to the support.

A further preferred method of the present invention is

A method of manufacturing a vertically aligned liquid crystal alignment layer;

A method of manufacturing a multi-domain vertical alignment of liquid crystal alignment layers;

To a method for manufacturing a liquid crystal alignment layer having a tilted optical axis

.

It is understood that the liquid crystal alignment layer of the present invention can also be used in the form of a polymer gel, a polymer network, a polymer film, and the like. The liquid crystal alignment layer can be used in the manufacture of unstructured or structured optical or electro-optical elements, preferably in the manufacture of hybrid layer elements.

The present invention also relates to a process for the preparation of a polymer or oligomer or polymer mixture or oligomer mixture by applying the photo-alignment composition according to the invention to a support, To a process for producing a liquid crystal alignment layer which is treated with light and is preferably isomerized and / or crosslinked by irradiation with alignment light.

A preferred method of the present invention is a method wherein a very specific region of the layer is aligned by selectively irradiating a specific region of the polymer layer or oligomer layer and / or by controlling the direction of irradiation of the alignment light, Lt; / RTI &gt;

The liquid crystal alignment layer is suitably prepared from a solution of a polymer or oligomer material. The polymer or oligomer solution is applied to a support optionally coated with an electrode (for example a glass plate coated with indium-tin oxide (ITO)). Different coating techniques such as spin-coating, meniscus-coating, wire-coating, slot-coating, offset-printing, flexo-printing, gravure-printing can be used in the process. Subsequently, or optionally after the preceding imidization step, the area to be oriented is irradiated with, for example, a high-pressure mercury vapor lamp, a xenon lamp or a pulsed UV laser, using a polarizing plate and optionally a mask for generating a structural image.

In addition, the present invention relates to the use of a liquid crystal alignment layer according to the present invention, which is preferably in a cross-linked form, as an alignment layer for a liquid crystal.

In addition, the present invention preferably relates to the use of a liquid crystal alignment layer for inducing vertical or planar alignment of adjacent liquid crystal layers, in particular for operation of the cell in MVA mode.

The irradiation time depends on the output of the individual lamps and varies from a few seconds to several hours. However, photoreaction (dimerization, polymerization, cross-linking) may also be performed by irradiating the homogeneous layer using, for example, a filter that allows only the passage of radiation for the cross-linking reaction.

It is understood that the liquid crystal alignment layer of the present invention can be used in the manufacture of an optical or electro-optical device having at least one orientation layer and an unstructured and structured optical element and a multilayer system.

The present invention relates to the use of a liquid crystal alignment layer in liquid crystal alignment.

Preferably, it is used in the induction of the vertical orientation of the adjacent liquid crystal layer.

A further aspect of the invention relates to an optical or electro-optic device comprising a photo-alignment layer according to the invention, preferably in cross-linked form. The electro-optic device may comprise more than one layer, preferably two layers. The layers or respective layers may contain one or more regions having different spatial orientations.

A further aspect of the invention relates to unstructured or structured optical and electro-optical components, preferably liquid crystal display cells, multilayer and hybrid layer devices, comprising at least one liquid crystal alignment layer as described above.

In addition, the present invention preferably relates to the use of a liquid crystal alignment layer for inducing vertical alignment of adjacent liquid crystal layers, in particular for operation of the cell in MVA mode.

The use of liquid crystal alignment layers to induce vertical alignment or planar alignment of adjacent liquid crystal layers is desirable.

A further preferred aspect of the invention relates to an optical or electro-optic device comprising at least one liquid crystal alignment layer. The electro-optic device may comprise more than one layer. The layers or respective layers may contain one or more regions having different spatial orientations.

The use of a liquid crystal alignment layer for optical and electro-optical elements is further preferred.

More preferably, the present invention relates to an unstructured or structured optical and electro-optical component, preferably a liquid crystal display, comprising at least one liquid crystal alignment layer, such as a polymer layer, a copolymer or an oligomer layer according to the invention Cell, multilayer and hybrid layer devices.

An optical component, system or device generates, manipulates or measures electromagnetic radiation.

BACKGROUND OF THE INVENTION Electro-optic components, systems or devices operate by the modification of the optical properties of materials by electric fields. This is therefore related to the interaction of the material's electromagnetic (optical) and electrical (electronic) states.

The optical or electro-optical component may be a waveguide, a security or brand protection element, a bar code, an optical grating, a filter, a retarder, a compensation film, a reflective polarizing film, Anisotropically scattering film compensator and retardation film, twisted retarder film, cholesteric liquid crystal film, guest-host liquid crystal film, monomer corrugated film ), A smectic liquid crystal film, a polarizing plate, a piezoelectric cell, a thin film exhibiting nonlinear optical characteristics, a decorative optical element, a luminance enhancement film, a component for wavelength-band selective compensation, , Components of a multi-view liquid crystal display, achromatic phase retarder, polarization correction / adjustment film, parts of optical or electro-optical sensors, A patterned reflective circular polarizer, a patterned reflective polarizer, and a patterned MC (monomeric pleated film) with anisotropic absorber, a component for a light-based telecommunication device, a patterned G / H polarizer with anisotropic absorber (But not limited to).

A security element, a compensation plate and a retardation film are preferable.

The advantages of the present invention were unpredictable to those skilled in the art. Surprisingly, it has been found that high alignment qualities can be achieved using the photo-alignment compositions of the present invention. Also, quite surprisingly, the production of thin liquid crystal alignment layers that meet the requirements of homogeneous, clear films has been made possible by the photo-alignment compositions of the present invention.

Example

Abbreviations for solvents:

NMP: 1-methyl-2-pyrrolidone (cas: 872-5O-4)

BC: 2-butoxyethanol (butyl cellosolve) (cas: 11-76-2)

IBIB: isobutyl isobutyrate (cas: 97-85-8)

The polymer formed was characterized by its intrinsic viscosity and NMR data. Some representative signals were seen in NMR. The integration is provided as a relative value.

Synthesis of polymer

Polyamic acid 1

(3.66 mmol) of [4 - [(E) -3 (3,6-dimethyl- - [[5-amino-2- [4-amino-2 - [[(E) -3- [4- [4- (4,4,4- trifluorobutoxy) benzoyl] oxyphenyl] Phenyl] methoxy] -3-oxo-prop-1-enyl] phenyl] -4- (4,4,4-trifluorobutoxy) benzoate . Followed by stirring at 0 ° C for 2 hours. The mixture is then reacted at room temperature for 21 hours. The polymer mixture was diluted with 18 mL of THF, precipitated with 800 mL of deionized water and dried under vacuum at room temperature, and then polyamic acid 1 was obtained in the form of a white powder having an intrinsic viscosity [?] Of 0.50 dL / g.

Polyamic acid 2

(4E) -3- [2- (2,4-diaminophenyl) ethoxy] -3-oxoprop-1-enyl} 3 - [[5-amino-2- [4-amino-2 - [[(E) -3- [4- [ Benzoyl] oxyphenyl] prop-2-enoyl] oxymethyl] phenyl] phenyl] methoxy] -3-oxo- prop- 1-enyl] Phenyl] 4- (4,4,4-trifluorobutoxy) benzoate as a diamine in a molar ratio of 7/3, polyamic acid 2 was obtained in the form of a white powder having an intrinsic viscosity [?] Of 0.33 dL / g do.

Polyamic acid 3

The polyamic acid 3 was synthesized in the same manner as the polyamic acid 1, using 4- (4-aminophenoxy) aniline and 1,2,3,4-cyclobutanetetracarboxylic dianhydride, to give an intrinsic viscosity [?] Of 0.37 dL / g &lt; / RTI &gt; in the form of a white powder.

Polyamic acid 4

Similarly to the synthesis of the polyamic acid 1, the polyamic acid 4 was obtained as a white powder having an intrinsic viscosity [?] Of 0.56 dL / g using 4- (4-amino-2-methyl- In powder form.

Manufacturing of formulations

Formulation 1

7.0835 g of a 30% solution of polyamic acid 1 in NMP is added to 201.875 g of a 20% solution of polyamic acid 3 in NMP. 108.042 g of NMP and 183.02 g of BC are added. The mixture is stirred for 30 minutes and filtered through a 0.2 [mu] m PTFE-filter to provide Formulation 1.

Formulation 2

7.0836 g of a 30% solution of polyamic acid 1 in NMP is added to 201.872 g of a 20% solution of polyamic acid 3 in NMP. 108.043 g of NMP, 137.25 g of BC and 45.75 g of IBIB are added. The mixture is stirred for 30 minutes and filtered through a 0.2 [mu] m PTFE-filter to provide Formulation 2.

Formulation 3

11.65 g of a 30% solution of polyamic acid 2 in NMP is added to 157.52 g of a 20% solution of polyamic acid 4 in NMP. 144.85 g of NMP and 139.6 g of BC and 46.52 g of IBIB are added. The mixture is stirred for 30 minutes and filtered through a 0.2 [mu] m PTFE-filter to provide Formulation 3.

Application example

Offset printing is performed on the Nakan E-400 MIZ with the following parameters:

Coating speed 20 m / min (condition 1), or 25 m / min (condition 2)

- Anilox roll speed 20 m / min (condition 1), or 25 m / min (condition 2)

- Anilox NIP 5 to 8 mm

- Table NIP 10 to 15 mm

- Anilox - Scrubber pressure 0.48Mpa

The coated substrate is dried on a hot plate at 80 DEG C for 1.5 minutes and then at 200 DEG C for 40 minutes.

Substrates used for testing (Conditions 1 and 2):

- Asahi Glass PD200 with a thickness of 0.3 mm

- ITO coated Asahi glass (sputter deposited SiO ₂ 200 nm / ITO 20 nm)

- Color filter (CF)

The coating quality is controlled and is listed in the table below and the surface quality is evaluated as "very good, defect free", "slight mura, several defects", "no defect," and " 1 to 4, respectively; Leveling is denoted as 1 to 4, respectively, corresponding to "very good", "good", "bad" and very poor, and thus poor leveling indicates de-wetting, .

table:

Example of "Defects Across the Surface" In Figure 1 of Formulation 1 coated on CF, microscopic defects can be found throughout the coated surface.

Examples of " superior coatings with very good leveling "in Figure 1 of Formulation 2 coated on CF.

Claims (18)

As a photo-alignment composition,
a) at least one single photo-alignment polymer, preferably a homopolymer or copolymer, having at least one photoreactive group; And preferably further polymers which do not have photoreactive groups, and b) at least one single solvent of formula I
&Lt; / RTI &gt;
Formula I
(R-CO-O-R ')
In the formula (I)
R and R 'are independently from each other straight chain alkyl or branched chain alkyl; Provided that at least one alkyl chain is branched. The photo-alignment composition of claim 1 comprising c) an additional polymer that does not have photoreactive groups. 4. The composition of claim 1 or 2 comprising: a) at least one single solvent of formula (I).
Formula I
(R-CO-O-R ')
In the formula (I)
R and R 'are independently straight-chain C ₁ -C ₆ alkyl or branched C ₁ -C ₆ alkyl and the other; Provided that at least one alkyl chain is branched. 4. The photo-alignment composition according to any one of claims 1 to 3, comprising at least one single solvent of formula (I).
Formula I
(R-CO-O-R ')
In the formula (I)
R and R 'are simultaneously branched chain alkyl. 5. The photoresist composition according to any one of claims 1 to 4, wherein the photoreactive group is a dimerizable, isomerizable, polymerizable and / or crosslinkable group; Preferably the photoreactive group is selected from the group consisting of cinnamate-, coumarin-, quinoline-, azo-, stilbene-, cyanostilbene-, chalcone-, diphenylacetylene, benzylidene- phthalimidine, benzylideneacetophenone, Stilbazole, and / or an azo-group. 6. The composition of any one of claims 1 to 5, comprising at least one single photo-alignment polymer comprising at least two monomers, wherein at least the monomer comprises photoreactive groups. 7. A composition according to any one of claims 1 to 6 comprising at least one single photo-alignment polymer comprising at least two monomers having photo-reactive groups. 8. The composition of any one of claims 1 to 7, further comprising a polymer which does not have photoreactive groups, including a backbone that is a polyamic acid, a partially imidized polyamic acid, a polyimide, a polyamic ester or a polysiloxane &Lt; / RTI &gt; 9. A photo-alignment composition according to any one of claims 1 to 8, further comprising a polymer having no photoreactive group, having the same backbone as the photo-alignment polymer. 10. A composition according to any one of the preceding claims, comprising at least one single photo-alignment polymer in an amount of from 0.5 to 50% by weight of the total weight of said photo-alignment polymer and said polymer not having photoreactive groups. &Lt; / RTI &gt; 11. A photo-alignment composition according to any of the preceding claims, comprising d) at least one further polar solvent which is an aprotic or protic polar solvent. 12. A process as claimed in any one of claims 1 to 11, wherein at least one aprotic polar solvent, preferably two aprotic polar solvents, more preferably N-methylpyrrolidone (NMP) or Methylpyrrolidone (NMP) and 2-butoxyethanol (BC) or N-ethylpyrrolidone (NEP) and at least one solvent selected from N-ethylpyrrolidone (NEP) 2-butoxyethanol (BC). &Lt; / RTI &gt; 13. A composition according to any one of the preceding claims wherein the solvent (I) and optionally further solvents are present in a total amount of 99 to 70% by weight, based on the total weight of the composition. 14. A composition according to any one of claims 1 to 13, further comprising at least one surfactant. A method of making a liquid crystal alignment layer comprising applying a photo-alignment composition according to any one of claims 1 to 14 to a substrate by printing or coating. 15. A liquid crystal alignment layer comprising a photo-alignment composition according to any one of claims 1 to 14 or prepared by the process according to claim 15. The use of the liquid crystal alignment layer according to claim 17 in optical and electro-optical elements. An optical and electro-optical element comprising the liquid crystal alignment layer according to claim 16.

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